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ICIQ Institut Català d’Investigació Química Av. Països Catalans, 16 43007, Tarragona, Spain Phone.: +34 977 920 200 Fax: +34 977 920 224 iciq@iciq.es | www.iciq.es Text: ICIQ Institut Català d’Investigació Química Graphic Design: MAFS DISSENY | www.mafsdisseny.com DL: T-1190/2010


Summary Letter from the Director . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1 About ICIQ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 1.1 Structure & Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2 Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.1 Research Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2.2 Research Support Area. . . . . . . . . . . . . . . . . . . . . . . . . . . . 72 2.3 Current Projects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 3 Scientific Output. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 3.1 Publications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.1 ICIQ Journal Covers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 4 Technology Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.1 Crysforma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 4.2 Esteve – ICIQ Joint Unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 4.3 Joint Projects with Industry . . . . . . . . . . . . . . . . . . . . . . . . 97 4.4 Patents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 5 Education & Scientific Outreach . . . . . . . . . . . . . . . . . . . 101 5.1 ICIQ Seminars Programme . . . . . . . . . . . . . . . . . . . . . . . . 102 5.2 Summer School. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 5.3 ICIQ Fellowships Programme. . . . . . . . . . . . . . . . . . . . . . 106 5.4 Master in Synthesis and Catalysis. . . . . . . . . . . . . . . . . . 107 5.5 Dissemination Activities . . . . . . . . . . . . . . . . . . . . . . . . . . 108 5.6 Newsletter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 APPENDIX I : Board of Trustees and Scientific Board. . . . . . 113 APPENDIX II : Staff Distribution. . . . . . . . . . . . . . . . . . . . . . . . 114 APPENDIX III : 5-Year Evaluation 2009. . . . . . . . . . . . . . . . . . 115 APPENDIX IV : Funding Evolution . . . . . . . . . . . . . . . . . . . . . . 117 APPENDIX V : PhD Thesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

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4


Letter from the Director

The year 2009 showed growth and confirmation of our ex-

We are also committed to a research model based on the col-

ceptional performance as one of the top level institutions for

laboration of different research groups, both at internal and

chemical research in Europe. Coinciding with our fifth anniver-

external levels, in order to contribute to the solution of complex,

sary, the second phase of our building was inaugurated. This

relevant problems. As a result of this strategy, ICIQ is impor-

new building already houses the computational groups and

tantly represented in the Spanish Consolider-Ingenio 2010

research groups under ICIQ's Tenure Track programme and

Programme, coordinating the Intecat project for the develop-

also provides new labs for the set up of up to 6 technological

ment of an integrated approach to catalysis, and significantly

spin-off companies in the context of the Science and Technology

participating on the Photomol project on photovoltaic energy.

Park of Tarragona. Moreover, throughout the year, three new

We are also involved in seven collaborative research projects

group leaders, Profs. Paolo Melchiorre and Kilian Muñiz, and Dr.

of the 6th and 7th Framework Programmes of the European

José Ramón Galán-Mascarós, have joined the Institute (in fact,

Union (among them, an ERC Starting Grant awarded to Prof.

by early 2010 Prof. Vladimir Grushin and Dr. Atsushi Urakawa

Emilio Palomares –PolyDot project– and in early 2010, an ERC

joined ICIQ as well). But ICIQ's excellence has been also reinforced

Advanced Grant given to Prof. Piet van Leeuwen and an ERC

by the positive assessment of the evaluation committee that

Starting Grant awarded to Dr. Núria López). The collaboration of

reviewed ICIQ's scientific and administrative performance during

different research groups has been also stimulated by funding

its first five years of activity (see appendix III). Finally, we have

three ICIQ strategic projects as part of ICIQ's policy in tackling

succeeded in carrying out pre-business and business initiatives

meaningful research areas.

derived from the Institute’s capacity for research and develop-

And last but not least, we are well aware of the importance

ment. The technology unit Crysforma and the Esteve-ICIQ Joint Unit are good examples and from our present perspective, we can also take the example of the Henkel-ICIQ Joint Unit that was set up in May, 2010 and a future technology unit for the development of catalysts that will start its activities by October, 2010.

of training future researchers; our PhD and Summer fellowships programme, Summer School and Seminar programme are already consolidated. Additionaly, ICIQ actively participates in the graduate studies of Universitat Rovira i Virgili as a Research Institute affiliated to this University. As a proof of

There is still a long way to go. We don't forget our endeavor to

our input the ICIQ/URV Master on Synthesis and Catalysis has

identify how chemical research can contribute to overcome the

started running in 2009/10.

problems and challenges our society is facing at the outset of

In short, we work hard for the development of our mission:

the 21st century. To provide responses to these challenges, we aim at leading chemical research in Catalonia, playing a main role in the transformation of our society towards a knowledgebased economy.

"to lead, from the perspective of molecular science, transversal strategies for the solution of socially and economically relevant problems, with the aim of contributing to the development of a knowledge-based economy and the improvement of the

In the field of molecular science, we identify some research fields

quality of life of the citizens".

such as catalysis, molecular nanotechnology and renewable

I hope the information we have collected in this report reflects

energy as key elements for the achievement of this long term goal. Research on renewable energies is the fastest growing

our efforts towards this direction.

field in our Institute. At a different level, we also recognize as a key element for this profound transformation, the incorporation of talented young researchers to the science and technology system of Catalonia. Our Tenure Track programme has so far allowed the creation of six new research groups at the Institute.

Miquel À. Pericàs

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1

About ICIQ T

he Institute of Chemical Research of Catalonia (ICIQ), conceived with the aim of becoming a reference centre for

Chemistry within the European Research Area, is the research institute that provides the talent and leadership needed to improve citizens’ quality of life through the application of chemistry at the frontiers of knowledge. Our mission is to lead, from the vantage point of molecular science, cross strategies for solving major social and economical problems, thereby contributing to the establishment of a knowledge-based economy and improving citizen’s quality of life.

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1. ABOUT ICIQ Structure and Strategy

1.1 Structure and Strategy

The ICIQ headquarters are located in a functional building with a built-up area of 12.800 m2. The site is equipped with all the latest safety devices and was built according to the same principles of sustainability that underlie the research conducted inside. Some of the building’s stand-out features include minimal water and energy consumption, comprehensive laboratory management and a modular design that enables the restructuring of laboratory spaces to accommodate different needs. This year 2009, the inauguration and start-up of activities of the new building (ICIQ Phase II), have increased the number of research, research support and technology laboratories. The new building provides a more strategic location to house the computational groups and research laboratories dedicated to the ICIQ’s two main strategic objectives. To this end, one floor of the new building is part of the Science and Technology Park of Tarragona (Parc Científic i Tecnològic de Tarragona, or PCTT) and it is used to house a business incubator and joint ICIQ/ industry units; and another floor hosts research groups from the ICIQ’s Tenure-Track Programme for Researchers.

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1. ABOUT ICIQ Structure and Strategy

The Institute of Chemical Research of Catalonia is a private foundation governed by the following bodies: The Board of Trustees is the senior body with regard to the representation, governance and administration of the foundation. Board members include representatives of the Government of Catalonia (DIUE), Universitat Rovira i Virgili (URV) and the members of the ICIQ's foundation partners: Laboratorios Esteve, Repsol-YPF, Bayer and Basf. (See appendix I). The Scientific Advisory Board is the body responsible for counselling the Board of Trustees on the foundation’s scientific policy and for evaluating its activities and it is made up of national and international prestigious professionals in the field of chemistry. (See appendix I). The Business Advisory Board, formed by the body for participation by the ICIQ foundation’s partner institutions from the chemical and pharmaceutical sector (Repsol-YPF, Bayer, BASF and Laboratorios Dr. Esteve) and its function is to assist with aspects relating to the transfer of the results generated by the ICIQ to the business sector.

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The Director, based on the instructions of the Board of Trustees, defines the main guidelines for the ICIQ’s scientific policy, takes the initiative with regard to the Institute’s strategic projects and, together with the Scientific Advisory Board, is responsible for selecting and evaluating the ICIQ’s scientific team. As part of the Direction’s area, the Communication and Image Unit coordinates ICIQ’s institutional relations and all the institute’s promotion and marketing tasks. The ICIQ has an efficient and flexible organisation, with capacity of fast response to new industrial research demands, a scientific team of excellence, modern and sophisticated equipment and an efficient knowledge & technology transfer. After five years in operation, 207 people (see appendix II) are working at the Institute, which is structured in four major areas: The Research Area is comprised of seventeen research groups, each one of them headed by a Group Leader, who handling a variety of issues using complementary methodological approaches, guarantees a multidisciplinary approach to real


1. ABOUT ICIQ Structure and Strategy

Management Area

chemical problems. Besides, this year, the new Vicedirection for Academic Affairs has been created in order to coordinate the education policy of ICIQ and scientific activities as symposiums, seminars etc. as well.

Foundation’s human resources and assets and for implemen-

The Management Area is a flexible and dynamic structure specifically designed to facilitate sound management of all administrative aspects. It is likewise responsible for managing the

& Maintenance and Human Resources, which has been

ting its budget. It is divided into five small-scale units designed to meet specific needs: Purchasing & Logistic Support, Accounting, Information Technology, Quality, Safety, Environment created this year 2009 after the recommendations of ICIQ’s evaluation committee.

Direction Office

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1. ABOUT ICIQ Structure and Strategy

Strategic Area

The Strategic Area is dedicated to the implementation of two of ICIQ’s crucial principles: generating competitive revenue to fund its activities, and promoting knowledge and technology transfer from the ICIQ to industry. The Area consists of three units: Resources with the mission to support the institute in the generation of competitive resources from research funding programs at the regional, national and European level; Industrial Property, responsible for the management of intellectual property (IP) generated at the institute and the subsequent IP transfer to industry; and Business Development with the mission of actively promoting collaborations with industry. The Research Support Area includes the most up-to-date advances in each instrumental field required to support the research carried out at the Institute by the different research groups and technology platforms and it is currently formed by seven units: X-ray Diffraction, Nuclear Magnetic Resonance, High Resolution Mass Spectrometry, Chemical Reactions Technologies, Chromatography, Thermal Analysis & Electrochemistry, Heterogeneous Catalysis, Photophysics and Spectroscopy & Reaction Kinetics. Quality Research, Innovation and Technological Upgrade are our challenges. ICIQ has a strong expertise in the performance of target-oriented R&D projects, especially in the fields of Catalysis (homogeneous and heterogeneous), Molecular Recognition (design of receptors, new materials, design of specific sensors, probes, inhibitors/stabilisers, separation agents, drug delivery systems), Nanoscience and Renewable Energies.

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The strategic lines of the Institute affords fundamental importance to its excellent research team which, after passing rigorous selection and assessment criteria, are provided with sufficient material and human resources to develop its research programme. The ICIQ is particularly proud of its Tenure Track Programme, which started in 2005, giving to excellent young researchers the chance to begin an independent career. It is a unique initiative in Catalonia and in Spain, a platform for the promotion of these researchers in their years of highest scientific creativity. Furthermore, this programme guarantees the renewal of the Institute’s research lines. In 2009 Dr. José-Ramón Galán-Mascarós has joined ICIQ as group leader within this Tenure Track Programme. It is also expected that Dr. Atsushi Urakawa joins ICIQ as a Tenure Track researcher in early 2010. The Institute aspires to consolidate its finances through the research results in order to guarantee its economical feasibility throughout time. In this sense, the industrial protection of these research results and their transfer are a very important tool. For example, in 2009, the ICIQ’s Technology Transfer strategy has resulted in the creation of a Technology Development Unit, Crysforma, oriented to give scientific and technological support in the field of pharmaceutical solid state development. Moreover, two collaborative research projects with industry have evolved into Joint Industry-ICIQ Units, one with a large national pharmaceutical laboratory (Esteve-ICIQ) and another, which is expected to start its activities in 2010, with a multinational chemical company (Henkel-ICIQ).


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Research

T

he Catalysis of Chemical Process and its contribution to sustainable chemistry represents the Institute’s most

extensive research line with the general aim to develop processes and products which minimise waste. It comprises research into all spheres of chemical catalysis: homogeneous, heterogeneous and enantioselective catalysis, the development of new ligands and catalytic processes and the design and simulation of catalytic reactors. Another area of research is centered on Nanoscience and Supramolecular Chemistry, primarly geared toward designing molecular receptors, self-replicating and selfassembling molecules, molecular aggregates with specific properties (sensors, molecular motors, etc), molecular materials combining chemical and physical properties, and supramolecular catalysts. The general aim is to contribute to the development of molecular nanotechnology through a bottom-up approach. And last but not least, the fastest-growing line of research at ICIQ, is focused on the field of Renewable Energies and Environmental Research, with the aim to contribute to the obtention of clean energy sources from a chemical standpoint. Several groups are currently working on developing organic solar cells to serve as an alternative to the silicon cells used today, and doing research to find new strategies for environmental remediation.

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2.1 Research Groups

ICIQ Group Leaders

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Prof.

Ballester

RESEARCH GROUP

Group Leader: Pau Ballester Postdoctoral Researchers: Marcos Chas / Francisco Muñoz (until Sept.) / Eddy Martin / Begoña Verdejo (until Oct.) PhD Students: Guzmán Gil / Moira Ciardi / Laura P. Hernández / Mónica Espelt / Virginia Valderrey Visiting Students: Zack Mesinger (Mar. – Jul.) / Rubén Tejero (Jun. – Sept.) / Pascal Blondeau (Aug. – Dec.) / Elisabetta Iengo (8 – 14 Mar.) Administrative Support: Beatriz Martín

lo-porphyrins. We exploit the coordination prop-

O

adequate template dimerize to form a molecular

ur research is mainly focused in the design, synthesis and study of functional molecu-

lar aggregates. We tackle the thermodynamic characterization of self-assembly processes as a methodology to construct large and functional multimolecular architectures. To this end, we make an extensive use of porphyrins and metal-

erties of metallo-porphyrins with amine ligands to induce the self-assembly process. Another area of our interest resides in the design and application of molecular containers. These are molecules or supramolecules which are sufficiently large to include or encapsulate other molecules. We prepare self-complementary calix[4]pyrroles, that in nonpolar solvents and in the presence of capsule. We investigate the effect that the confinement of molecules in reduced nanoscopic spaces may have in modifying their chemical reactivity. We also use these molecular containers as new physical organic chemistry tools to quantify weak intermolecular interactions.

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2. RESEARCH Prof. Ballester Research Group

Self-assembly of functional multimolecular aggregates The molecular self-assembly of macrocycle 4 is induced by the simultaneous coordination of two molecules of 4-pyridyldiphenylphosphine 3, a highly selective ditopic ligand, to Zn-bisporphyrin 1 and a square-planar Pd(II) complex 2 ·COD.

with the equation to evaluate the statistical (noncooperative) self-assembly equilibrium constant. We used numerical methods (SPECFIT program) to predict the solution behavior (speciation) of two mixtures of the three molecules 1, 3, and 2 ·COD in a 1:2:1 relative stoichiometry at two different overall concentrations. The method uses the overall stability constant values and the stoichiometries of eleven species (complexes) implicated in the multicomponent equilibrium self-assembly of 4. Estimated stability constants of some of the species were statistically determined. The agreement observed between the theoretical simulations and the experimental data validates the suitability of the theoretical treatment of self-assembly macrocyclization in a three component

Strategy We have also reviewed the work carried out in our research group during the last ten years applying metal-mediated selfassembly processes to the construction of multiporphyrin functional assemblies. The construction of well-defined and discrete supramolecular structures resulting from self-assembly requires the use of multiple and separated connections operating in one or more close loops, consequently, the great majority of the multiporphyrin assemblies that we have prepared are of cyclic nature. We have placed special emphasis not only in the characterization in solution of the formed assemblies but also in the thermodynamic characterization of the assembly process and in the assessment of cooperativity.

Fig. 2 – Schematic representation of a self-assembled receptor.

Fig. 1 – Chemical structures of the molecular components used in the selfassembly of the heterobimetallic macrocycle 4 studied in this work. CAChe minimized structures of the cyclic assemblies with trans coordination geometry in the external metal center (Pd). Nonpolar hydrogen atoms are removed for clarity. The Zn and Pd metal centers are shown as CPK spheres.

We have reported a detailed thermodynamic characterization of the assembly process based on the quantification of each one of the two metal(Zn,Pd)-ligand(N,P) pairwise binding interactions implicated in the supramolecular macrocycle and its effective molarity value (EM). The experimental values of the pairwise metal-ligand interactions have been derived from UV-vis, NMR titrations, and isothermal titration calorimetry experiments of reference model systems. In turn, an EM = 1 × 10-2 M has been determined by relating the experimental overall stability constant determined for the cyclic assembly

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We have also described examples in which functionality has been derived from the three dimensional structure of multicomponent assemblies. We have also described the thermodynamic characterization of the assembly process of a covalently connected trimeric Zn porphyrin 5 induced by coordination to a bipyridyl functionalized perylene bisimide 6. The bispyridyl ligand acts as pillars via two axial coordination bonds with the porphyrinic Zn(II) ions fixing the planes of the porphyrin units in a nearly co-facial orientation and inducing the formation of trigonal prism-like structures. The fully assembled 52·63 aggregate and the partially assembled one, 52·62, in which only two zinc porphyrin sites of trimeric 5 are axially coordinated to 6, are present in solution in equilibrium with freely diffusing species 1 and 2. The strong quenching observed in the mixture for the luminescence of the components 6 and 5 is ascribed to an efficient photoinduced electron transfer from the Zn porphyrin units of 5 to coordinated 6 occurring upon excitation of both components within the assemblies. In the formed assemblies, the Zn porphyrin units of the trimer 5 behave completely independent. Thus, the porphyrin units that are not


2. RESEARCH Prof. Ballester Research Group

Fig. 5 – Left) Chemical structures of the receptors and the pyridine N-oxides. Reaction conditions: i) BrCH2COOMe, K2CO3, DMF; ii) LiOH,H2O; iii) H+; iv) 3-Bromopropylphthalamide, NaH; v) NH2NH2. Right) X-ray crystal structure (side and top views) of the inclusion complex 9⊂7. Hydrogen atoms of 7 are omitted for clarity.

Fig. 3 – Molecular structures of the trisporphyrin 5 and bipyridyl functionalized perylene bisimide 6.

complex geometry in which the polar group is buried deep inside the aromatic cavity. A similar binding behavior is observed in acetonitrile. The geometry assigned to the inclusion complexes in solution has also been determined by X-ray analysis of single crystals of the 2⊂1a complexes grown in acetonitrile solution.

coordinated with 6 in the partially assembled complex, 52·62, display the same photophysical behavior registered for freely diffusing 5. The rate of charge separation within the cage is nearly independent on the polarity of the solvent (ca. 1010 s-1) whereas the charge recombination process, leading to the ground state, has a lifetime of 110 ps in dichloromethane and ca. 6 ns in toluene, in agreement with a Marcus inverted behavior.

Fig. 6 – Changes in the 1H NMR spectra during the titration of 7 and 8 with 9a in water-d2 at pD = 7.3. See Figure 5 for proton assignments.Primed letters are assigned to the proton signals in the 1:1 complex.

Molecular encapsulation and self-assembled dimeric capsules

Fig. 4 – Side view of the minimized structures of assemblies 52·63. For clarity non-polar hydrogens and the p-pentyl groups of the meso phenyl substituents in 5 have been omitted. 6 is represented with the van der Waals surface.

Molecular Recognition in water We have reported the synthesis of two new water-soluble calix[4]pyrroles 7 and 8 containing four carboxylic and four amino groups respectively. The complexation studies of 7 and 8 with N-oxides 9a-b carried out using 1H NMR and UV-vis spectroscopy revealed that both receptors are able to form 1:1 inclusion complexes in water. The resulting complexes are highly stable kinetically and thermodynamically. The combination of hydrophobic binding with the formation of hydrogen bonds provide the major driving forces for the complexation of pyridine N-oxides in water yielding a

We have prepared two self-complementary calix[4]pyrroles 10a-b that, in non-polar solvents and in the presence of an adequate template (i.e. 4,4’-bipyridine bis-N,N’-dioxide 11), dimerize through the formation of a circular belt of eight hydrogen bonded ureas and additional hydrogen bonding interactions between the polar ends of 11 and the two binding sites of the calixpyrrole components. The overall result is the formation of a ternary inclusion complex showing very high thermodynamic and kinetic stability. Furthermore, the system we have described constitutes one of the few examples of supramolecular cages containing endohedral hydrogen bonding functionality for potential ordering included guests. Future achievements for capsules of this sort are in progress and will include their templated formation in the presence of guests capable of producing tetramolecular complexes, as well as the formation of mixed calixarene-calixpyrrole tetraurea hybrid capsules.

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2. RESEARCH Prof. Ballester Research Group

Fig. 9 – Molecular strcutures of the componds used in the development and testing of the SC-ISE. Left) Two views of the energy minimized structure of the complex between the octaamide cavitand and acetylcholine.

Fig. 7 – Molecular structures of compounds 10 and 11. The 10·10 dimers are shown schematically.

electron-rich aromatic surfaces of the synthetic host result in the formation of complexes with highly kinetic and thermodynamic stability. The positive charge of choline (2-hydroxyethyl-trimethylammonium) and the roughly spherical shape of its trimethylammonium group fits to the negative charges on concave surfaces provided by the octaamide cavitand.

Fig. 8 – Energy minimized structure of the heterodimeric capsule 10a·10b encapsulating one bipyridine bis-N-oxide 11. 11 is shown as CPK, the molecular component 10b is displayed as a VDW surface and 10a in stick representation. Some hydrogen atoms are omitted for clarity.

Molecular Recognition at work In collaboration with the group of Prof. F. Xavier Rius at the University Rovira i Virgili we have developed a new solid-contact ion selective potentiometric electrode (SC-ISE) for the determination of choline and derivates in aqueous solution.. The conjunction of the octaanide cavitand receptor 12 synthesized in our group, as the molecular recognition element, and a network of single-walled carbon nanotubes (SWCNT), acting as solid transducer material, has been the backbone of this new potentiometric sensor. The octaamide cavitand is a well known synthetic receptor highly selective for biologically important tetraalkylammonium cations (i.e., choline 13, acetylcholine 14, and carnitine 15) and allows the selective binding of these compounds in solution. The guest-host interaction takes place in the acrylate polymeric matrix that constitutes the ion-selective membrane (ISM) of the solid-contact electrode. Cation-π attractions between the positive charge of the guest and the

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Fig. 10 – Top: The different parts of the solid-contact ISE. Bottom: Schematic representation of the different layers deposited onto the top of the glassy carbon rod (SWCNT and ISM) and the representation of the main transduction process.

As can be observed in Figure 10, three main sections can be distinguished in the electrode developed: the ion-selective membrane (ISM), the SWCNT layer and the glassy carbon as conducting substrate. The acrylate polymeric membrane, containing the octaamide cavitand (ionophore) and choline tetrakis(4-chlorophenyl)borate as lipophilic anion, in contact with the test solution, allows the primary ion choline to be distributed between the two immiscible phases. As a consequence


2. RESEARCH Prof. Ballester Research Group

of the fast equilibrium established, a boundary potential is generated at the aqueous/organic interface that depends on the logarithmic activity of choline ion in the aqueous solution. The layer of SWCNT functions as a transducer providing a high stability in the potentiometric signal, converting the ionic current in the polymeric membrane to the electronic current that flows through the glassy carbon conducting rod. Figure11 illustrates the EMF signal recorded after successive additions of the target analyte. It can be observed that the signal has a stable behaviour, without perturbations and random noise after each addition. In each case, when the concentration increases the response time decreases. At intermediate values of total concentration of choline, such as 10-3.5 M, the time response was less than 1 minute, while at the lowest concentration values the time response was around 10 minutes

Articles ºº“Determination of choline and derivatives with a solid-contact ion-selective electrode based on octaamide cavitand and carbon nanotubes.” Biosens. Bioelectron 2009, 25(2), 344-349. Ampurdanes, Jordi; Crespo, Gastón A.; Maroto, Alicia; Sarmentero, M. Ángeles; Ballester, Pablo; Rius, F. Xavier. ºº“Thermodynamic Characterization of the Self-Assembly Process of a Three Component Heterobimetallic Bisporphyrin Macrocycle”. J. Phys. Chem. B. 2009, 113(33), 11479-11489. González-Álvarez, Almudena; Frontera, Antoni; Ballester, Pablo. ºº “Metal-mediated multiporphyrin functional assemblies.” J Porphyr. Phthalocya. 2009, 13(4-5), 481-493. Hernandez, Laura P.; González-Álvarez, Almudena; Oliva, Ana I.; Ballester, Pablo. ºº“Self-assembly of dimeric tetraurea calix[4]pyrrole capsules. ” P. Natl. Acad. Sci. U.S.A. 2009, 106, 10455-10459 Ballester, Pablo; Gil-Ramírez, Guzmán.

Fig. 11 – EMF responses of the choline solid-contact ISE over time for increasing total concentrations of choline in the testing solution, expressed in logarithmic units. In the insets the stability of the signal and the response time can be observed at low (top left) and high (bottom right) concentration values

The limit of detection measured for the SC-ISE could allow the determination of choline in biological samples as blood Noncarboxylated single-walled carbon nanotubes were used for the first time as solid transducer and displayed a similar behaviour to the carboxylated nanotubes. Importantly, the solid nature of the transducer will allow the complete miniaturization of the electrode.

ºº“Self-assembly of double-decker cages induced by coordination of perylene bisimide with a trimeric Zn porphyrin: study of the electron transfer dynamics between the two photoactive components.” Dalton Trans. 2009, (20), 4023-4037. Oliva, Ana I.; Ventura, Barbara; Wurthner, Frank; Camara-Campos, Amaya; Hunter, Christopher A.; Ballester, Pablo; Flamigni, Lucia. ºº“Cyclic oligomers based on complementary Zn(II) and Sn(IV)-porphyrins.” New J. Chem. 2009, 33(4), 777-783. Metselaar, Gerald A.; Ballester, Pablo; de Mendoza, Javier. ººMolecular Recognition of Pyridine N-Oxides in Water Using Calix[4]pyrrole Receptors. J. Am. Chem. Soc. 2009, 131(9), 3178-3179. Verdejo, Begoña; Gil-Ramírez, Guzmán; Ballester, Pablo.

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Prof.

Bo

RESEARCH GROUP

Group Leader: Carles Bo Postdoctoral Researchers: Simon Pierrefixe / Mickaël Gicquel PhD Students: Pere Miró / Cristina Pubill Technicians: Martín Gumbau / Joan Iglesias Administrative Support: Núria Vendrell

and homogeneous catalysis related issues: character-

O

systems, assessment of non-bonding interactions

ur research deals with the application of computational chemistry methods to a variety of

themes, in most cases in close collaboration with experimental groups at ICIQ and at other institu-

tions. The topics fall into three main categories: - Structure and reactivity of organometallic compounds

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ization in-silico of reactive intermediates, elucidation of reaction mechanisms, origin of the chemo-, regio- and enantioselectivity, ligand effects, ligand design and structure-selectivity relationships. - Supramolecular Chemistry: structure of host-guest and supramolecular catalysis. - Polyoxometalates (POMs): electronic structure, mechanism of catalytic oxidation reactions, dynamic structure of cations and solvent water molecules around and inside POMs.


2. RESEARCH Prof. Bo Research Group

Homogeneous Catalysis The hydroacylation reaction is an atom-economical, transition metal catalysed process that yields a ketone from an aldehyde and an alkene, via C-H bond activation of the aldehyde followed by insertion of the alkene (Fig. 1). This year we completed a joint project in collaboration with Prof. Castillón (URV), in which we investigated in detail the mechanism for the rhodiumphosphine catalyzed hydroiminacylation of alkenes. This study applied NMR spectroscopy and DFT-based methods to characterise the molecular structures of the involved intermediate species, and to evaluate the thermodynamics and energy barriers of the rate-determining step, namely, the oxidative addition. Moreover, both cationic and neutral systems were considered (Ref.1).

the reaction products promotes the back reaction and therefore, low conversions are obtained. On the other hand, and also in collaboration with a group of experimentalists (Prof. Otero, UCM, Ciudad Real), we studied the effect of auxiliary ligands on the structure of hybrid scorpionate /cyclopentadienyl Ti and Zr complexes. We found that the number of alkoxide and/or imido ligands largely infuenced the isomeric equilibrium, and determined the most stable species. It is worth mentioning that, although we used model systems, our results were in complete agreement with the X-Ray data (Ref.2).

Polyoxometalates The structure and reactivity of polyoxometalates (POMs) is an important branch of our research activities, for which the group holds worldwide recognition. We use here a variety of tools to handle these molecular anionic metal-oxide systems of increasing complexity. DFT-based methods profit from the high symmetry often present. Molecular dynamics simulations enable studying the distribution of cations around the anions and the structure of water molecules inside and outside POMs. Two of the papers published this year (Refs. 3, 4) were selected to illustrate the cover of some journals.

Fig. 1 – Hydroacylation reaction and proposed mechanism for the rhodiumphosphine catalysed hydroiminacylation of alkenes.

With neutral systems, the oxidative addition step was shown to be thermodynamically favoured. With the cationic system, the oxidative addition reaction was shown to be endothermic by DFT calculations and NMR experiments did not detect the corresponding intermediate. The energy barriers in the cationic and in the neutral pathway were relatively similar. Fig. 3 – Cover pages

Both papers dealt with the famous ball-shaped nanocapsule Mo132 (Fig. 4), formed by 132 molibdenum atoms and with formula [{[MoMo5O21(H2O)6]}12{Mo2O4(SO4)}30]72-. Indeed, the nanocapsule presents 12 large Mo9O9 pores in its surface, where other ions and solvent water molecules can pass through. In collaboration with Prof. Weinstock (BGU, Israel) a remarkable phenomenon was reported (Ref. 3): carboxylates negotiate passage through the Mo9O9 pores of the 3 nm diameter. Branched-alkane-substituted carboxylate “guests” enter the host/capsule even though they are larger than the size of the capsule’s metal oxide pores. Further studies are being carried out at present to understand this phenomenon better. On the other hand, a cluster of 100 water molecules has been described inside the nanocapsule.

Fig. 2 – Molecular structures of two isomers of a hybrid scorpionate /cyclopentadienyl complex.

This indicated that the role of chloride when it is coordinated to the rhodium complex is to increase the stability of the oxidative addition product, enabling the reaction to continue. This is not the case in the cationic complexes, since the low stability of

When guanidinium cations close the pores of the capsule, a highly organized water structure is formed, which consists of three layers that correspond to platonic polyhedrons (icosahedron, dodecahedron) with 20, 20 and 60 molecules (vertexes) in each layer. In collaboration with Prof. Müller (U. Bielefed, Germany), the structure of the water cluster inside the capsule was studied. The equivalent system, in which the HCOO- groups substitute

19


2. RESEARCH Prof. Bo Research Group

the SO42- groups, thus decreasing the charge from -72 to -42, was considered since the water cluster structure is slightly different in this new capsule. Indeed, it has been observed that a fourth layer of water molecules appears.

Fig. 6 – Most probable locations for cations on the Mo57V6 surface from MD simulations.

Fig. 4 – Polyhedral representation of Mo132 with HCOO- linkers (O: red, C: black).

We succeeded in reproducing both the number and location of the water layers inside the nanocapsule, and the shape of the polyhedra described experimentally. Moreover, a new kind of internal motion of the water cluster was suggested that is nowadays a topic of further research. Our simulations (Ref. 4) thus demonstrated that differently functionalized capsules induce the spontaneous self-assembly of confined high and low density water.

process that Nature performs easily. The design of synthetic systems capable of water oxidation in aqueous solution poses a formidable challenge. In this quest, ruthenium complexes occupy a prominent role. Among them, Meyer’s “blue dimer”, cis,cis-[(bpy)2(H2O)RuIIIORuIII(H2O)(bpy)2]4+ was the first one described in literature. Very recently, Prof. Bonchio (Padova, Italy) reported a ruthenium-substituted polyoxometalate that can perform the reaction under smooth conditions. The new compound is formed by a tetra-ruthenate core Ru4O6 (see Fig. 7), which is stabilised by two POMs molecules, with formula [RuIV4( μ-O)4(μ-OH)2(H2O)4(γ-SiW10O36)2]10-. The mechanism of the reaction was not well understood, therefore, we started a joint collaboration with the group in Padova, and obtained spectroscopical, electrochemical and computational evidence for the different intermediates. We proposed a four electron oxidation process that brings the four ruthenium atoms from the initial Ru(IV) oxidation state to the final Ru(V), which is the competent state to form the new O-O bond. (Ref. 6)

Fig. 5 - Two representations of the anion [H3Mo57V6(NO)6O183(H2O)18]21-.

Also in collaboration with the group of Prof. Müller, we studied the oxomolybdate [H3Mo57V6(NO)6O183(H2O)18]21- (Fig. 5), which is an ideal system because of its intermediate size and its high symmetry (D3h). We were interested here in investigating the possibility of cations entering the small cavity through a pore of similar diameter as the one in Mo132. Molecular dynamics simulations enabled obtaining the most probable locations of cations. In none of the simulations, neither Li+ nor Na+, cations passed through the pore but remained in particular positions very close to the anion surface, as indicated by yellow regions in Fig. 6. These results stimulated new X-Ray diffraction experiments where amonium and potasium cations were precisely located at the locations we predicted (Ref. 5). This is an unprecedented example of Supramolecular Chemistry on a cluster surface, where ammonium ions were selectively trapped by crown-ether-like macrocycles. One of the most prominent applications of POMs is in catalytic process because of their ability to mediate in electron transfer reactions, for example water oxidation, which is a

20

Fig. 7 – Schematic formation [RuIV4( μ-O)4(μ-OH)2(H2O)4(γ-SiW10O36)2]10-

and

structure

of

From the results of molecular dynamics simulations, it is possible to extract instant configurations of the solvent and the counter-ions around the solute. We demonstrated that all this information could be used to develop an explicit solvent model for highly charged species such as polyoxometalates. The model includes solvent molecules in the first solvation shell explicitly, and long-range bulk effects and counter-ions as


2. RESEARCH Prof. Bo Research Group

a set of single point charges. The model strongly stabilises the electronic structure of the Keggin anion. The energies of the Kohn-Sham orbitals obtained using our model lie very close to those computed using COSMO continuum solvent model; moreover, the total solvation energy evaluated with our model compares well to the value calculated by COSMO (Ref. 7). Finally, we also contributed to the implementation of a numerical algorithm to integrate the electronic charge density and associated fields in the atomic regions defined by the theory of atoms in molecules (Ref. 8).

Articles ºº“Rhodium-Catalyzed Intermolecular Hydro-iminoacylation of Alkenes: Comparison of Neutral and Cationic Catalytic Systems” Organometallics 2009, 28, 2975- 2986 P. Marcé, C. Godard, M. Feliz, X. Yáñez, C. Bo, S. Castillón ºº“Hybrid scorpionate/cyclopentadienyl titanium and zirconium complexes with alkoxide and imido ligands” Inorg. Chim. Acta 2009, 362, 2909-2914 A. Otero, J. Fernández-Baeza, A. Antiñolo, J. Tejeda, A. LaraSánchez, L. F. Sánchez-Barba, M. Sánchez-Molina, C. Bo, M. Urbano-Cuadrado ºº“Flexible Pores of a Metal Oxide-Based Capsule Permit Entry of Comparatively Larger Organic Guests” J. Am. Chem. Soc. 2009, 131, 6380- 6382 A. Ziv, A. Grego, S. Kopilevich, L. Zeiri, P. Miró, C. Bo, A. Müller, I. A. Weinstock

ºº“Gated and differently functionalized (new) porous capsules direct encapsulates’ structures: Higher and lower density water” Chem. Eur. J. 2009, 15, 1844 - 1852 T. Mitra, P. Miró, A. R. Tomsa, A. Merca, H. Bögge, J. Bonet Ávalos, J. M. Poblet, C. Bo, A. Müller ºº “Supramolecular Chemistry on a Cluster Surface: Fixation/ Complexation of Potassium and Ammonium Ions with Crown-Ether-Like Rings” Angew. Chem. Int. Ed. 2009, 48, 5934- 5937 A. Müller, F. L. Sousa, A. Merca, H. Bögge, P. Miró, J. A. Fernández, J. M. Poblet, C. Bo ºº“Water Oxidation at a Tetraruthenate Core stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence to trace the Competent Intermediates” J. Am. Chem. Soc. 2009, 131, 16051-16053 A. Sartorel, P. Miro, E. Salvadori, S. Romain, M. Carraro, G. Scorrano, M. di Valentin, A. Llobet, C. Bo, M. Bonchio ºº“Towards a computational treatment of polyoxometalates in solution using QM methods and explicit solvent molecules” Can. J. Chem. 2009, 87, 1296 -1301 P. Miró, J. M. Poblet, J. Bonet Ávalos, C. Bo ºº“A high performance grid-based algorithm for computing QTAIM properties”

Chem. Phys. Lett. 2009, 472, 149 -152 J. I. Rodríguez, R. F. W. Bader, P. W. Ayers, C. Michel, A. W. Götz, C. Bo

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Prof.

de Mendoza RESEARCH GROUP

Group Leader: Javier de Mendoza Postdoctoral Researchers: Matthew P. Conley / Augustin de la Croix / Caterina Lubinu / Vera Martos (until Dec.) / Geert Metselaar (until Jul.) / Sara Pasquale / Eva Santos (Oct. – Dec.) / Yong Yang PhD Students: Berta Camafort / Elisa Huerta / Ondrej Kundrat / Philipp Reeh / Alla Shadrova (until Sept.) / Julián Valero Administrative Support: Núria Sugranyes Technician: Aritz Durana Visiting Students: James Cooper (Summer Fellow Jul.-Sept.)

continued our efforts to develop ligands from the se-

T

3). Coordination chemistry has been employed for

he research carried out in our group focuses on supramolecular chemistry, at the interfaces

of both biology and materials sciences. In a fruitful European Union network (ACSEPT project), we have

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lective extraction of actinides and lanthanides from the nuclear waste (ref. 1). Most of our work deals however with biology-related topics. New oligoguanidinium scaffolds have been designed to cross the cell membranes and a new strategy for the synthesis of such structures by a solid phase protocol has been developed (ref. 2). For the selective binding to the surface of proteins we have employed calixarenes designed to selectively and reversibly block the entrance of the potassium channels (ref. self-assembly of porphyrin arrays, using as the design principle the different coordination properties of Zn(II) and Sn(IV) (ref. 4).


2. RESEARCH Prof. de Mendoza Research Group

New calixarenes as deep cavities and dendrimers One of the aims of this project is to prepare stable cavities from calix[4]arenes by deepening their inherent cavities through the attachment of large, flat aromatic surfaces at the wider rim, which can be bridged by metal ions and carbon chains. These conical, deeper and more rigid cavities could encapsulate suitable guests as it has been recently demonstrated for a calix[4]arene-based metallocavitand of nanoscopic dimensions (Figure 1) for which calix[4]arenes and cavitands without substituents on the lower rim are ideal guests. Recently, other metals, such as palladium and platinum have been employed as assembling elements at the corners of the pyramidal structure. In addition, these corners can be linked by carbon bridges, by means of a four-fold, transition-metal catalyzed cross-metathesis reaction. The resulting rigid structures are optimal hosts for other calixarenes, as revealed by X-ray crystallography. Although these constitute unpublished results, most of this work has been finished and will be submitted for publication shortly.

self-assembled 2D and 3D structures, such as rosettes or capsules are only formed at high concentrations and/or in the presence of suitable guests, provided fragments are hold together through multiple robust interactions such as hydrophobic forces, hydrogen-bonded networks and/or metals. Our group was pioneer in the field more than one decade ago.

Fig. 3 – A hydrogen-bonded, self-assembled dimeric capsule for the selective separation of fullerenes without chromatography.

Fig. 1 – A rhenium-based, rigid metallo-cavitand of nanoscopic dimensions for the encapsulation of calixarenes.

New calix[6]arene-based dendrimers functionalized at position 5 of the spacer arm between opposite rings have been prepared. These congested structures can reach space congestion after just one generation (Figure 2). Interconnecting spacers can be functionalized with binding sites (ureas, receptors for squarates, or cis/trans isomerizable azo groups), leading to novel receptors or sensors for molecular recognition.

Fig. 2 – X-ray structure of a calix[4]arene linked to four calix[6]arenes.

Self-assembly Self-assembly is a common feature in biology and a current pursuit of supramolecular chemistry and material sciences for the construction of nanometer scale structures. In solution,

The remarkable binding properties of 2-ureido-4-[1 H]-pyrimidinone (UPy), one of the strongest hydrogen-bonded selfcomplementary motifs, can be used to construct rosettes, cavities or functionalized polymers stabilized by quadruple hydrogen bonds in a favorable DDAA sequence. Thus, selfassembled capsules based on UPy were recently described by us and highlighted in previous yearly reports. A well-defined dimeric capsule of nanoscale dimensions by combining the curvature of cyclotriveratrylene (CTV) and three high-affinity hydrogen-bonding UPy units (Figure 3, left). The resulting spherical host encapsulates a fullerene molecule within its large cavity with a high selectivity for C84 and C70 over C60 (Figure 3, right). By simple solid-liquid extractions, C70 with a purity of 97% could be obtained from fullerite after only two runs, without chromatography. Furthermore, since enriched mixtures of higher fullerenes (C76-C84) are also obtained, we studied the direct selective removal of C84 from fullerite by solid-liquid extraction, since calculations and binding constant measurements revealed that C84 is an almost ideal guest for the cavity. Recent results show that a single molecule can arise when the two moieties are covalently linked together after the encapsulation event. This can be easily achieved by transition metal promoted crossed metathesis when the appropriate substituent (R = homoallyl) is introduced in the UPy subunits. As a result, the entrapped fullerene can not be released out of the cavity (molecular maraca, Figure 4), which has important consequences in the properties of the guest. Another topic of current interest in our laboratory is the design and study of defined multiporphyrin arrays, in an attempt to mimic the intriguing natural system called the light-harvesting complex, which converts sunlight in chemical energy by a large number of chlorophyll molecules that are ingeniously positioned in circular arrays (ensuring a maximum energytransfer). To this aim, combinations of Sn(IV), Zn(II) and Al(III) containing porphyrins, endowed also with complementary functions at the meso positions to axially bind intermolecularly

23


2. RESEARCH Prof. de Mendoza Research Group

Fig. 4 – Synthesis of a molecular maraca with an encapsulated fullerene.

to the central metal of another porphyrin have been evaluated as self-assembly systems. A recent result deals with a combination of Zn(II) and Sn(IV) in the appropriate porphyrin framework results in a cyclic decameric structure (Figure 5, ref. 4).

folds, which are small enough to deeply penetrate the extracellular vestibule (the “turret loop”) of the potassium channels, with its lower rim oriented towards the pore, as is shown in Figure 6. Electrophysiology experiments on modified frog oocytes have revealed that the ligands act as efficient reversible blockers for the channel (ref. 3). Currently we explore the possibility of achieving selectivity, i.e. to develop ligands that specifically block one of the voltage dependent K+ channels (such as Kv1.1 or Kv1.2, etc) without interfering with the others. This is the ultimate goal of this research, with deep connections with drug design.

Fig. 6 – A tetracationic calixarene interacting at the extracellular vestibule of a potassium channel.

Membrane carriers

Fig. 5 – Sn(IV)-porphyrin 1, Zn(II)-porphyrin 2 and their proposed cyclic decameric self-assembled aggregate [1·2]5

Protein-ligand interactions An outstanding protein surface which retains quaternary symmetry and interacts with cationic ligands is the selectivity filter and the pore region of potassium channels. These are key elements in neurotransmission as they conduct K+ ions across the cell membrane, down the electrochemical gradient and underlie processes like hormone secretion, cell volume regulation and electrical impulse formation. Many diseases, mostly nervous system disturbances, are linked to malfunction of these channels. In collaboration with D. Trauner and E. H. Isacoff (University of California at Berkeley) we have designed and tested several four-fold symmetric ligands based on cationic calix[4]arene scaf-

24

We showed recently that oligomers of bicyclic guanidines can be useful cell penetrating agents. In particular, tetraguanidinium strands easily internalize and localize in mitochondria. This was further established my means of an emissive terbium conjugate to show that tetraguanidines localize into mitochondria, although they cause apoptotic cell death. These studies were developed in collaboration with D. Parker (Durham, UK). More recently we focused on the internalization of our oligoguanidinium strands (Figure 8) attached to modified DNA derivatives, such as peptide nucleic acids, the so-called PNAs, which are DNA mimics with a pseudopeptide backbone with the nucleobases. This offers interesting perspectives in drug delivery of antisense nucleic acids (gene therapy). The work is being carried out in collaboration with Peter E. Nielsen (Univ. of Copenhagen, DK). In view of the interesting properties of oligoguanidinium strands, we have developed new synthetic methodologies to have an easier access to this important series of compounds.


2. RESEARCH Prof. de Mendoza Research Group

Articles ºº(1) “Bismalonamides (BISMA) as new extractants for Am(III) and Eu(III) from aqueous high-level wastes.” Solvent Extraction and Ion Exchange 2009, 27, 107-131. Murillo M. Teresa, G. Espartero Amparo, Sánchez-Quesada Jorge, de Mendoza Javier, Prados Pilar. ºº(2) “Solid-phase synthesis of chiral bicyclic guanidinium oligomers.” Journal of Combinatorial Chemistry 2009, 11, 410-421. Vera Martos, Pilar Castreño, Miriam Royo, Fernando Albericio, Javier de Mendoza. ºº(3) “Calix[4]arene-based conical-shaped ligands for voltage-dependent potassium channels.” Proceedings of the National Academy of Sciences of the USA 2009, 106, 10482-10486. Vera Martos, Sarah C. Bell, Eva Santos, Ehud Y. Isacoff, Dirk Trauner, Javier de Mendoza.

Fig. 8 – Molecular structures of the oligoguanidinium-PNA conjugates synthesized.

One of these approaches is a solid phase synthesis strategy. The proposed methodology is novel on two fundamental aspects: it reports on the application of chiral bicyclic guanidinium monomers in the context of solid phase and constitutes the first example of solid supported synthesis of thioethers conceptually following the Merrifield approach. Our approach is based on the iterative attack of a resin-bound thiolate which reacts with a synthon via an SN reaction. Disulfide bonds generated during coupling under basic conditions are reduced by dithiothreitol treatments of the resin, and non complete anchorage of the guanidinium monomer is tackled by a capping protocol with benzyl bromide. In addition, the strategy is enriched by semi-permanent protecting groups that enable, through orthogonal anchorage protocols, the linkage of potential cargo molecules (ref. 2).

ºº(4) “Cyclic oligomers based on complementary Zn(II) and Sn(IV)-porphyrins.” New Journal of Chemistry 2009, 33, 777-783. Gerald A. Metselaar, Pablo Ballester, Javier de Mendoza.

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Prof.

Echavarren RESEARCH GROUP

Group Leader: Antonio M. Echavarren Postdoctoral Researchers: Kian Molawi / Dirk Spiegl / Julien Ceccon / Nolwenn Martin / Francesco Camponovo / Dominic Janssen (until Mar.) / Sergio Pascual (until Jan.) / Thorsten Lauterbach (until Nov.) PhD Students: Mihai Raducan / Paula de Mendoza / Ana Escribano / Patricia Pérez-Galán / Verónica LópezCarrillo / Claudia de León / Núria Huguet / Madeleine Livendahl / Anthony Pitaval / Nicolas Delpont / C. Rogelio Solorio / Elena Herrero-Gómez (until Jul.) Technicians: Vanessa Martínez Visiting Students: José Antonio Blanco (Jul. – Sept.) / Maria Kirillova (Jun. – Aug.) / Ángeles Mosquera (Apr. – Jun.) / Zoraida Ramiro (Sept. – Oct.) Administrative Support: Sònia Gavaldà

26

O

ur group centers on the discovery of new synthetic methods based on the use of

transition metals as catalysts (organometallic

chemistry directed towards organic synthesis "OMCOS" ). In particular, in the last few years, we have focused our work on the development of new reactions using gold catalysts for the activation of small molecules and in the application of these reactions for the synthesis of complex, biologically active natural products. We also work on the development of new strategies for the synthesis of nanographenes and related molecules of importance in material science.


2. RESEARCH Prof. Echavarren Research Group

Gold Catalysis The recent outburst of activity in homogenous gold catalysis has largely centered on exploiting the alkynophilicity of cationic gold(I) complexes in intramolecular processes. In this context, gold(I)catalyzed cyclizations of 1,6-enynes 1 have been the benchmark for the development of new gold-catalyzed reactions (Figure 1). These reactions proceed through distorted cyclopropyl gold carbenes 2 as intermediates and give rise to adducts 3 in the presence of heteronucleophiles (water or alcohols) or carbon nucleophiles such as electron-rich arenes and heteroarenes, 1,3-dicarbonyl compounds, and allylsilanes add to 1,6-enynes with Au(I) catalysts. In the absence of nucleophiles, 1,6-enynes 1 evolve by three major pathways via skeletal rearrangement to give products 4 (single exo-cleavage), 5 (double exo-cleavage), and 6 (single endo-cleavage). 1,7-Enynes react with Au(I) by similar pathways. Cyclobutenes 7 resulting from intramolecular [2+2] cycloaddition process have also been obtained from 1,6-, 1,7-, and 1,8-enynes. A different type of cyclobutenes 8 have been obtained in the Pd-, Pt-, and Au-catalyzed cyclization of enynes.

are the very active catalysts in a variety of transformations. Thus, gold complexes with N-heterocyclic carbene ligands, such as A and B (Figure 3) have been shown to be very selective catalysts for the activation of enynes. Related complexes with open carbene ligands have also been prepared. Gold complexes with bulky dialkylbiarylphosphine ligands such as C-E are stable white crystalline salts that can be stored under ordinary conditions. Complex E has been used in the intermolecular cyclopropanation of alkenes with diazocarboxylate derivatives. The reactivity of cationic complexes C-E towards alkynes is only surpassed by that of highly electrophilic cationic complex F, which bears a bulky phosphite ligand.

Fig. 3 – Cationic gold(I) catalysts.

Fig. 1 – Gold-catalyzed cyclization of 1,6-enynes.

Our research group has proposed simple mechanisms for the Au(I)-catalyzed reactions of enynes in which the single cleavage rearrangement takes place through 9 to give rise to 1,3-dienes 4 in a stereospecific transformation (Figure 2). In the double cleavage rearrangement, a new Au(I) carbene 10 is formed, which gives rise to 1,3-dienes 5 by a 1,2-H shift and demetalation. Compounds of type 6 are formed by a variation of the single-cleavage mechanism.

1,6-Enynes 12 substituted with alcohols, ethers, or silyl ethers at the propargylic position react with gold(I) catalysts by a new type of intramolecular 1,5-migration of OR groups to give tricyclic compounds 13 in a stereospecific process (Figure 4). In this reaction, intermediates 14 form α,β-unsaturated gold carbenes 15 that undergo intramolecular cyclopropanation reactions with the pendant alkene. This reaction is general and simple enynes with OR substituents at the propargylic position such as 16 also react leading to intermediates that react intermolecularly with the alkenyl chain to form 17. Related intermolecular reactions and C-H functionalization processes have been also observed.

Fig. 2 – Mechanisms for the gold(I)-catalyzed skeletal rearrangement of 1,6-enynes.

The neutral donating ligand in cationic complexes [AuL]+ can play a very significant role in gold catalysis. We have developed a series of cationic gold(I) complexes with differently donating ligands that

Fig. 4 – 1,5-Migration of OR groups.

27


2. RESEARCH Prof. Echavarren Research Group

In contrast, substrates 18 with a carbonyl group in the alkenyl chain react with Au(I) to form oxatricyclic compounds 19 (Figure 5). In this reaction, fragmentation is also observed as a minor pathway leading to ketones 20. Now, based on this transformation, we have developed a conceptually new reaction between 1,6-enynes 21 and carbonyl compounds that proceeds in an intermolecular fashion to give dienes 22 and acetone in a metathesis-type process.

Importantly, the propargyl stereocenter in enyne 23 controls the formation of the new three stereocenters. The synthesis of related sesquiterpene pubinernoid B (25) was also achieved using a similar strategy staring from the Z-isomer of 23. Finally, as a part of a program towards the synthesis of lundurin B (26), a new alkaloid with a new structure isolated from plants of the genus Kopsia, we have reported the reaction of indoles such as 27 to form tetracyclic compounds 28 in an unusual 8-endo-dig cyclization process catalyzed by AuCl3 (Figure 7)

Fig. 7 – Model for the synthesis of lundurin B.

Articles ºº“Gold-catalyzed olefin cyclopropanation.” Tetrahedron 2009, 65, 1790-1793. (“Symposium in Print” Catalysis using Gold Complexes). Prieto, A.; Fructos, M. R.; Díaz-Requejo, M. M.; Pérez, P. J.; PérezGalán, P.; Delpont, N.; Echavarren, A. M.

Fig. 5 – Gold(I)-catalyzed cyclization of oxo-enynes and metathesis-type synthesis of dienes

The synthesis of oxatricyclic compounds of type 19 has been applied in the key step in the first stereoselective total synthesis of (+)-orientalol F (24) (Figure 6).

ºº“Gold-Catalyzed Reactions of 1,5- and 1,6-Enynes with Carbonyl Compounds: Cycloaddition vs. Metathesis.” Chem. Eur. J. 2009, 11, 5646-5650. Escribano-Cuesta, A.; López-Carrillo, V.; Janssen, D.; Echavarren, A. M. ºº“Evolution of Propargyl Ethers into Allyl-Gold Angew. Chem. Int. Ed. 2009, 48, 6152-6155. Cations in Cyclizations of Enynes.” Jiménez-Núñez, E.; Raducan, M.; Lauterbach, T.; Molawi, K.; Solorio, C. R.; Echavarren, A. M. ºº“Synthesis of the Tetracyclic Core of the Lundurines by a Gold-Catalyzed Cyclization.” Tetrahedron 2009, 65, 9015-9020 (“Symposium in Print” “Modern Applications of Transition Metal Catalysis in Heterocycle Synthesis). Ferrer, C.; Escribano-Cuesta, A.; Echavarren, A. M. ºº“Carbene or cation?” Nature Chem. 2009, 1, 431-433. (Invited News and Views). Echavarren, A. M.

Fig. 6 – Synthesis of orientalol and pubinernoid B.

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ºº“Stereoselective Gold-Catalyzed Cycloaddition of Functionalized Ketoenynes: Synthesis of (+)-Orientalol F.” Chem. Commun. 2009, 7327-7329. Jiménez-Núñez, E.; Molawi, K.; Echavarren, A. M.


Dr.

Galán-Mascarós RESEARCH GROUP

Group Leader: José Ramón Galán-Mascarós Laboratory Technician: Vanesa Lillo PhD Students: Sara Goberna

O

ur team is devoted to research in Coordination Chemistry. From our experience in supramo-

lecular chemistry and molecular materials, we try to tackle the synthesis, structural and physical characterization and processing of a variety of moleculebased compounds of interest in Materials Sciences (multifunctional materials) and Biology (models for metalloprotein redox active sites).

Redox active peptide-supported metallic clusters In natural photosynthesis in the higher green plants, a complex reaction uses solar energy to convert H2O into O 2 and reducing equivalents. Photosystem I (PS I) uses the reducing equivalents to reduce CO2 to carbohydrates, while Photosystem II (PS II) is able to oxidize water at the oxygen evolving center (OEC), where O2 is released. In artificial photosynthesis, however, the main goal would be to use the solar energy to produce oxygen and fuels such as H2, formic acid or other hydrocarbon species. It can be easily envisioned that artificial photosynthesis would have a huge impact in many aspects of human life and economics. An efficient process would address (and probably solve) the energy problem for the foreseeable future, while being environmentally clean.

29


2. RESEARCH Prof. Galán-Mascarós Research Group

Water is not able to absorb light, therefore several subsystems will be needed for the whole process. In a modular approach, artificial photosynthesis can be achieved by constructing two catalytic sub-cells, one for hydrogen production and another one for water oxidation, connected to a chromophore through energy and electron transfer. Several systems have already shown to be good catalysts for hydrogen or hydrocarbon production. On the other hand, no good enough catalysts for the efficient oxidation of water are known. This is done quite efficiently in green plants, algae and cyanobacteria by the OEC in PS II. Although no accurate structure for the OEC has been determined, the data gathered by several groups says that it is formed by a cluster of four Mn centers supported by carboxylate and imidazolate groups in adjacent aminoacid units (Fig. 1). A synthetic analogue to the OEC of the PS II that possesses functional activity remains one of the greatest challenges in the field of bioinorganic chemistry. All Mn clusters (dimers, trimers or even tetramers) reported to date with related structures to the OEC are completely inactive as catalysts. Several catalysts for water oxidation have been developed, though. At present, only a few of them are manganese-based molecular species. The most efficient catalysts for water oxidation remain Ru complexes and metal oxides but the high cost and lack of stability of the former and the low efficiency of the latter are still key problems to overcome. Surprisingly, no peptide-based manganese cluster with redox activity has been reported, whereas such a species is obviously able to catalyze water oxidation in Nature.

Fig. 1 - Proposed structure for the OEC

Thus, our aim is to study the Coordination Chemistry of transition metal clusters with oligopeptides, in the search for stable and redox active polymetallic clusters able to be involved in the oxidation of water. From a structural point of view, many metal complexes with aminoacids have been reported but, surprisingly, very few oligopeptide complexes are known. Actually, the number of metalloprotein crystalline structures solved to date is much larger than those of metal-oligopeptides. Therefore, the information on structure and reactivity of oligopeptides with metals will also be very valuable to understand the interaction of metals with proteins, that control many of the biological processes in the fields of Medicine and Biology.

Multifunctional molecular materials Optically active materials are target compounds in different research fields. The interest is based on the added value of chirality and also in the possibility of appearance in such systems

30

of novel physical phenomena from its synergy with magnetic or electrical properties. This prediction deals with the intrinsic anisotropy of a chiral magnetic/electrical media, for example, in the presence of an external magnetic field. If the magnitude of this effect is large enough, these materials would have many applications, as they would work as optical/electrical rectifiers, tunable by external stimuli (magnetic field). Thus, we are studying the photo-magnetic and magneto-optical synergy in single molecules of metal complexes of high photophysical activity and high magnetic moment.

Fig. 2 - A double-decker lanthanide complex

Rare-Earth coordination chemistry Coordination chemistry of rare earth ions is a topic of increasing interest since it has been not conveniently explored in the last decades, when compared to that of transition metal ions. The striking properties of rare earths complexes are having a huge impact in different fields, including state-of-the-art technological applications: as MRI agents or as components of permanent magnets. We are studying the chemistry of lanthanide ions with phtalocyanine ligands and analogs, since these complexes (Fig. 2) are part of the family of the so-called Single-Molecule Magnets (SMMs), where magnet-like behavior is found in a single molecule, although usually at very low temperatures (close to liquid He). Among these materials, lanthanide double decker complexes still hold the high temperature record, showing SMM behavior close to the liquid N2 limit. We are also studying the chemistry of lanthanide ions with redox active polyoxometalates (POMs), to yield POM-supported mixed transition-metal / rare-earth complexes, as model compounds to study the magnetic interactions between these two types of magnetic centers.

Articles ºº “Anchoring of Rare-Earth-Based Single-Molecule Magnets on Single-Walled Carbon Nanotubes”

J. Am. Chem. Soc. 2009, 131, 15143-15151. S. Kayatskaya, J. R. Galán-Mascarós, L. Bogani, F. Hennrich, M. Kappes, W. Wernsdorfer, M. Ruben Dr. Galán Mascarós joined ICIQ in September, 2009.


Dr.

Kleij

RESEARCH GROUP

Group Leader: Arjan W. Kleij Postdoctoral Researchers: Robert M. Haak / Antonello Decortes PhD Students: Sander J. Wezenberg / Daniele Anselmo / Giovanni Salassa Visiting Student: Danilo Misseri Technician: Ana M. Castilla Administrative Support: Marta Moya (until Dec.) / Ingrid Mateu

T

he research of our group focuses on the implementation of salen technology in new materials

and catalytic systems with new properties. Salen ligands and their complexes are characterized by a number of attractive features within the context of sustainability. Since 2006, we have progressively applied our knowledge to develop new (preferentially modular) routes to multinuclear salen compounds that have found application in cooperative

homogeneous catalysis, shape-persistant macrocycles, and new sensoring and templating devices. Presently, our main focus is on the development of new catalysis centred on the use of carbon dioxide as a renewable feedstock in (enantioselective) catalysis, and the use of multinuclear salen complexes in enantioselective multi-component reactions and cascade processes.

Reactivity studies Part of our research efforts have focused on the reactivity and stability of the Zn(II)-centred salphen family of salen systems [salphen = N.N'-bis(salicylidene)imine-1,2-diaminobenzene]. These complexes, as well a their multinuclear analogues, show high Lewis acidic behaviour (Figure 1) and consequently binding affinity for a range of N-donor and O-donor ligands and/or substrates. Recently we added another family of donor systems to this selection which are based on anions (vide infra).

31


2. RESEARCH Prof. Kleij Research Group

Various Zn(salphen) complexes have been subjected to a range of pyridine alcohol ligands to understand their potential to activate O-containing substrates (such as epoxides) in a catalytic fashion. These studies have revealed an interesting template mechanism for the formation of unusual trinuclear assemblies. These assemblies comprise a central Zn-complex consisting of two mono-deprotonated bis-2,6-dimethanol-pyridine ligands, and the anionic O-atoms are associated with two Zn(salphen) modules to generate the Zn3 assembled species.

Zn(salphen) and various epoxide-Zn(salphen) structures have been characterized by X-ray analysis. These studies have

Fig. 1 – Electrostatic energy surface for a Zn(II)salphen complex. In blue the electron-poor regions.

The template mechanism was studied in detail revealing that the initial step involves coordination of the O-atom of the pyridine alcohol. The reactivity towards a number of these substrates was tested and the structures of the resultant assemblies detailed and supported by X-ray crystallography (Figure 2) and NMR/MS studies. The template process has helped us to define suitable substrates for catalytic conversions, and we are currently focusing on the cycloaddition reaction of carbon dioxide to (terminal) epoxides, with a primary attention to enantioselective conversions under mild conditions with high selectivity for the monomeric carbonate. Our first set of results have proven the ability of the Zn(salphen) complex to catalyze this reaction at low temperature (45ºC) and pressure (10 bar) with ample scope (10 substrates) in the epoxide reagent (Figure 3). The Zn(salphen) complex proved to be essential for high activity at relatively low temperatures since other Zn(salen) complexes and a simple Zn salt [Zn(stearate)2] were practically inactive (Figure 3). The Zn(salphen) catalyst represents a cost-effective, modular, relatively green and stable catalyst for this process.

Fig. 2 – An unusual trinuclear Zn3 assembly obtained by Zn(salphen) templation and characterized by X-ray diffraction. The Zn-atoms are highlighted in yellow.

The involved mechanism, currently under investigation, is believed to start off with epoxide coordination to the

32

Fig. 3 – Catalyzed cycloaddition of carbon dioxide to epoxide using various Zn(salphen) structures.

supported the view that the co-catalyst of this process, i.e. NBu4I, is sterically hindered in the ring-opening step of the coordinated epoxide once doubly substituted substrates (epoxides) are employed. This finding was previously also observed for other metallosalens utilized as catalysts in the formation of cyclic carbonates. After having established the potential of the Zn(salphen) system as catalyst for this important reaction utilizing a renewable carbon feedstock (CO2) we are now directing our attention to asymmetric synthesis of these carbonates.

Multinuclear systems In a separate program we have also studied the Lewis acid behavior of these Zn(salphen) paying attention to their ability to form multinuclear structures. Our aim is to be able to access such multinuclear structrures in a controlled way as they are essential for the development of new cooperative processes and applications in important and challenging conversions such as enantioselective multi-component reactions. Our work in the field of metallosalen chemistry has revealed that the Zn ion, once ligated to the salphen ligand, provides a hemilabile complex which needs external ligand stabilization. Under certain conditions, especially when non-coordinating media are employed, the Zn-ion may be readily displaced by proton sources such as H2O and protic substrates. In a recent contribution we have demonstrated the ability of the Zn(salphen) scaffold to bind various anions. We have particularly focused on the acetate case, and studied the solution dynamics using UV-vis titrations and NMR spectroscopy. In conjunction with solid state analysis, we can conclude that the acetate anion is able to switch from its coordination mode thus forming 1:1


2. RESEARCH Prof. Kleij Research Group

complexes or 2:1 assemblies via a bridging of the anion using both O-atoms. This information is superimposable onto more relevant carboxylates such as proline, known for its organocatalytic potential. We have therefore also investigated the formation of proline-derived supramolecular structures (as a non-covalent analogue of Jörgensen´s catalyst), as these may find useful application in organic synthesis using the steric bulk of the coordinated Zn(salphens) as a discriminating tool in enantio-selectively controlled conversions (Figure 4). A major advantage with our system is that the bulk around the proline unit can be easily altered by introducing different substitutents in the salphen backbone. The supramolecular ´proline´ assembly is currently under investigation in catalysis where we focus on a benchmark reaction using an aliphatic aldehyde (e.g. cinnamaldehyde) and a suitable nucleophile (e.g. indoles).

an olefinic substrate into an epoxide which will then be subsequently transformed into a cyclic carbonate structure in a one-pot procedure. The presence of the two catalysts present in one structure holds promise for an efficient process, and the catalytic performance is measured against a combination of the two "free" metallosalens.

Fig. 5 – Modular approach toward heterobimetallic salen structures based on a 3,3'-diaminobenzidene scaffold.

Fig. 4 – Bidentate ligation of acetate to two Zn(salphen) complexes (X-ray, upper part left) and the analogous proline structure (energy-minimized structure, upper part right, Zn atoms shown in yellow). Note that the NBu4 cations are not shown.

Heterobimetallics The selective formation of heterobimetallic structures is a huge challenge. The presence of two distinct catalyst structures within one molecule is interesting from an efficiency point-of-view, and cascade processes may be designed utilizing the different properties of the metal ions. We have now succeeded in the selective formation of a series of heterobimetallic salen complexes with an ample scope in metal ion combination and peripheral substituents for electronic and steric modulation. Noteworthy is that also chiral information can be readily introduced making enantioselective conversions potentially possible. Our design is based on earlier work with the 3,3'-diaminobenzidene scaffold and has resulted, among many others, a bimetallic Zn-Mn structure such as depicted in Figure 5. These structures should be useful in cascade catalysis approaches; here we will focus on the conversion of

Fig. 6 – Macrocyclic tetranuclear salen complexes obtained in a template reaction. Below, a possible assembly mode is presented for the Zn4 species with two Zn(salphen) units forming dimers with a set of two Zn(salphen) fragments of another Zn4 molecule (tBu groups omitted for clarity).

Macrocyclic structures Our previous work with the 3,3'-diaminobenzidine scaffold has produced a series of diimines (see Figure 5, left) that have synthetic use if combined with the appropriate reagents. We reasoned that these diimines, when treated with 1,3-dihydroxy4,5-diformyl-benzene in the presence of a templating metal salt, would give access to tetranuclear macrocyclic systems. Indeed, the templated process selectively furnishes the macrocyclic compound in high yield (88%), while in the absence of the metal reagent virtually no product could be observed. The Zn4 macrocycle could be conviently transmetalated to give access to a small series of metallo-macrocycles (Figure 6) with

33


2. RESEARCH Prof. Kleij Research Group

distinct photophysical properties. The supramolecular aggregation was investigated by NMR and UV-vis spectroscopy and compared with a number of reference compounds. The combined data revealed that in the case of the tetranuclear Zn4 complex, the assembly behavior is predominantly determined by Zn(salphen) self-dimerization, i.e. each Zn(salphen) in Zn4 is potentially able to form dimers with a Zn(salphen) unit of another macrocycle through μ2-O bridging. In the assembled state, both the absorbance as fluorescence faetures are significantly reduced. A very large increase is, however, noted in polar media and in the presence of donor systems that are able to axially coordinate the Zn(salphen) fragments thereby breaking up the assembled state. A 20-fold increase in fluorescence between the assembled and de-assembled state was observed at 10-7 M for Zn4. This switching in assembled state can be used in sensoring applications. Alternatively, we assume that it may also be useful as a recycling tool since the solubility of the macrocyclic Zn4 complex is limited in apolar media. Therefore, we have tested the Zn4 complex in the formation of cyclic carbonates using epoxides and carbon doixide as reagents, and preliminary results show that this approach is indeed feasible. The self-assembly of the Zn(salphen) complexes has also been visualized at the single-molecule level on a graphite surface using scanning tunneling microscopy (STM, Figure 7).

Fig. 7 – Visualization of the self-dimerization of Zn(salphen) complexes at the single-molecule level using scanning tunneling microscopy (STM) imaging techniques. Abbreviations: D = dimer, M = monomer, V = vacant site.

Further spectroscopic studies with a large series of model complexes have revealed that the self-dimerization constant is in the order of 108 M-1, and that the mode of self-dimerization strongly depends on the substitution pattern of the salphen ligand (2010, in press).

Articles ºº“Isolation and Structural Characterization of a Binuclear Intermediate Species Pertinent to Transmetalation of Zn(salphen) Complexes and the Formation of Polynuclear Salen Structures” Inorg. Chem. 2009, 48, 846-853. L. San Felices, E. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Non-symmetrical Salen Ligands and Their Complexes: Synthesis and Applications” Eur. J. Inorg. Chem. 2009, 193-205. A. W. Kleij ºº“The Assembly of Supramolecular Boxes and Coordination Polymers Based on Bis-Zinc-Salphen Building Blocks” Chem.−As. J. 2009, 4, 50-57. M. Kuil, I. M. Puijk, A. W. Kleij, D. M. Tooke, A. L. Spek, J. N. H. Reek ºº“Access to Hybrid Supramolecular Salen-Porphyrin Assemblies via a Selective in situ Transmetalation-MetalationSelf-Assembly sequence” Inorg. Chim. Acta 2009, 362, 1053-1057. S. J. W ezenberg , G. A. M etselaar , E. C. E scudero -A dán , J. Benet-Buchholz, A. W. Kleij ºº“Anion-Templated Formation of Supramolecular Multinuclear Assemblies” Chem.−Eur. J. 2009, 15, 5695-5700 S. J. Wezenberg, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Trapping of a Four-Coordinate Zinc Salphen Complex inside a Crystal Matrix” Chem.−Eur. J. 2009, 15, 4233-4237. E. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

34

ºº“Templated Synthesis and Site-Selective Conversion of Completely Non-Symmetrical Bis-Metallosalphen Complexes” Eur. J. Inorg. Chem. 2009, 2467-2471. A. M. Castilla, S. Curreli, N. M. Carretero, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Zinc-Centred Salen Complexes: Versatile and Accessible Supramolecular Building Motifs” Dalton. Trans. 2009, 4635-4639. A. W. Kleij ºº“Ligation of Substituted Pyridines to Metallosalphen Complexes. Crystallographic Characterization of an Unexpected Four-Component Supramolecular Assembly Comprising a Sterically Demanding Ligand” Eur. J. Inorg. Chem. 2009, 3562-3568. E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Formation of unusual Zn-cluster compounds based on pyridinealcohol platforms” Dalton Trans. 2009, 7368-7373. D. Anselmo, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Formation of Unusual Trinuclear Assemblies: Scope and Mechanism of Zn(salphen) Templated Activation of Pyridine Alcohol Substrates” Eur. J. Inorg. Chem. 2009, 5307-5318. M. Martínez Belmonte, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij ºº“Modular Synthesis of Heterobimetallic Salen Structures Using Metal Templation” Org. Lett. 2009, 11, 5218-5221. A. M. Castilla, S. Curreli, E. C. Escudero-Adán, M. Martínez Belmonte, J. Benet-Buchholz, A. W. Kleij


Prof.

Llobet

RESEARCH GROUP

Group Leader: Antoni Llobet Postdoctoral Researchers: Chiara Dinoi (until Feb.) / Pau Farràs / Somnath Maji / Sukanta Mandal / Sophie Romain / Xavier Sala (until Mar.) / Laura Vigara PhD Students: Carlo Di Giovanni / Isidoro López / María Isabel López (until Sept.) / Takashi Ono / Nora Planas / Stephan Roeser / Josep Saurí (until Sept.) / Lydia Vaquer Administrative Support: Paula Segovia (until Nov.) / Agustina Gisbert

T

tive is to understand the various factors that affect catalyst’s efficiency and selectivity with special focus on the transition metal electronic structure and space disposition. Particular attention is being paid to the catalytic oxidation of water to molecular dioxygen, given the implications of this reaction for new energy conversion schemes based on artificial photosynthesis. The final objective of this route consists on the photo-production of hydrogen from water and sunlight.

he group carries out research in the field of redox catalysis using transition metal complexes. We

are interested in the oxidation and reduction of both organic and inorganic substrates, and mainly those that are of technological interest. Our overall objec-

Mother Nature uses a whole range of metalloproteins to carry out a wide variety of oxidation processes in a highly selective and efficient manner. Our general philosophical approach is inspired by nature’s extraordinary performance.

35


2. RESEARCH Prof. Llobet Research Group

Thus we develop our transition metal redox catalysts based on nature’s wisdom, mimicking her structural motives and reactivity strategies. Our catalyst development involves the interplay of a variety of disciplines including, synthetic organic and inorganic chemistry, spectroscopy, electrochemistry, kinetics and catalysis. The following are some of the topics we are currently involved in::

Catalysts for Artificial Photosynthesis The prediction for energy demand by the year 2050 is in the range of 30-50 TW which is more than a 100% increase with regard to what we have consumed by the year 2004. Furthermore, given the rate of CO2 increase and the catastrophic consequences this is producing to our planet, it is obvious that our society has an urgent need for a carbon-neutral renewable energy source. An attractive and clean energy vector to solve this problem could be H2, but while the storage and separation of hydrogen has already been achieved with certain degree of success, the question of where do we get a sustainable hydrogen source still remains to be answered. Nature has been using water and sunlight as a source of energy in its photosynthetic processes for a long time. Oxidation of water to O2, 2 H2O

O-O + 4H+ + 4e-

(1)

is the terminal reaction of photosystem II (PSII) in green plants which takes place at a polynuclear Ca-Mn4 complex. This reaction is a thermodynamically demanding reaction since EÂş = 1.23 V (vs. SHE) at pH = 0.0. On the other hand it is of tremendous molecular complexity from a mechanistic perspective, since it involves the oxidation of water by 4 H+ and 4 e- with the formation of an oxygen-oxygen bond. It is thus an important reaction to be modeled since efficient low molecular weight models can lead to a first step towards creating a clean renewable energy source. The mastering of the performance of this reaction is nowadays the bottleneck for the development of artificial photosynthetic devices, capable of producing H2 from water and sunlight. Thus it constitutes the key to access a clean renewable fuel such as H2, the energy vector of the future. We have recently prepared a family of dinuclear Ru-aqua complexes containing dinucleating polypyridylic ligands. These ligands are chosen because they enforce a particular metal preorganization and because they impose a delicate balance between the Ru-aqua entities. That is: they are sufficiently close so that they can interact to one another but at the same time they are sufficiently apart so that an oxo bridging reaction can not take place. The latter would be highly detrimental since it would basically kill the catalytic activity with regard to water oxidation. The higher oxidation states of this Ru dinuclear complexes have been shown to be active with regard to the oxidation of water to molecular dioxyen. We are currently studying the effects of electronic perturbations over the performance of the catalysts as well as the reaction mechanisms through which those reactions proceed. Furthermore, we are designing specific ligands and complexes that will allow us to discriminate between potential intramolecular versus intermolecular mechanisms involving water nucleofilic attack to a Ruthenium-oxo electrophilic entity.

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Fig. 1. Zero-Emission Fuel-Cell Bus.

The high thermodynamic potential required for a catalyst capable of oxidizing water to molecular dixoygen implicates that its active species will also be capable of oxidizing a wide range of organic compounds. Therefore intermolecular catalyst-catalyst deactivation is one of the main deactivation pathways. For this purpose we are designing new dinucleating ligands that maintain the intrinsic electronic and coordination abilities of the orginal ligands but that contain a functionalized group that is able to be attached into an oxidatively rugged solid support. This will bring about a restricted translational mobility that would avoid those undesirable intermolecular interactions. The combination of spectroscopic, electrochemical and mechanistic information allows us to design and develop new and more efficient water oxidation catalysts based on Ru complexes. Those complexes are to be integrated in complex solar cells in a serious first step towards a viable commercial application. We are also at the moment developing the parallel chemistry, substituting the Ru metal center by Mn, and modifying the ligands taking into account the specific chemistry of such a first raw transition metal. The aim here is to increase the velocity of the water oxidation process and to understand the reaction pathways through which they proceed.

Photochemical oxidation of organic substrates We are in the process of developing the adequate transition metal complexes that can be attached into TiO2 semiconductors, or alternatively into quantum dots, so that they can perform the oxidation of organic substrates with just sunlight.

Fig. 2. Proposed photo-oxidation scheme for organic substrates based on Ru complexes.


2. RESEARCH Prof. Llobet Research Group

This reaction concept benefits from the absence of a generally polluting and expensive chemical oxidant and also from the formation of H2 as a byproduct.

Selective chemical oxidation of organic substrates under mild conditions There is an important number of dinuclear copper-containing proteins that use molecular dioxygen to carry out a variety of oxidations, including the industrially relevant oxidation of cyclohexane to cyclohexanol. In this topic we are centering our efforts in the synthesis, characterization and reactivity of transition metal complexes using mononucleating and dinucleating ligands. The appropriate design of dinucleating ligands permits to situate two transition metals in relatively close proximity so that cooperation phenomena can take place as well as its fine tuning. These spatial effects combined with electronic effects, permit the generation of synergic phenomena and in some cases the viability of a given reaction that is not observable with a mononuclear complex. In nature a large number of metalloproteins exists, whose function consists on the breaking of O-O bonds under very smooth conditions, O-O

2 [O]

(2)

for its subsequent incorporation in a specific substrate with high efficiencies and selectivity. As an example the oxidation of methane to methanol can be cited catalyzed by MMO (methane monooxigenase), CH4 + O2 + AH2

MMO

CH3OH + H2O + A (3)

where AH2 represents an external reducing agent. At present the chemical industry carries out a number of oxidation processes in a stoichiometric as well as in a catalytic manner but with low efficiencies and selectivity. Besides in general, expensive, highly toxic and environmentally harmful substances are used as oxidants. Here we deal with the field of the activation of oxygen utilizing models inspired in the molecu-

lar engineering of non-heme processes developed by nature, that is conceptually the inverse reaction of water oxidation. Our objective is to elucidate the mechanisms through which these reactions occur in order to extract the key information to be able to design and build low molecular weight analogues. We are particularly interested in understanding the parameters that govern the intermolecular interaction between active species and external substrate. The key substrates we are dealing with at the moment are unsaturated hydrocarbons, alcohols, olefins and sulfides. With the last two ones we are also engaged in building up their corresponding chiral analogues to perform the catalytic oxidation in an enantioslective manner.

Supramolecular catalysis In this project we are combining molecular recognition with oxidative catalysis in order to achieve a selective functionalization of a given substrate, a process that nature also performs. The challenge here is to prepare non-symmetric bifunctional molecules that are geometrically designed so that they are capable to perform both tasks in a harmonized manner: the recognition process through a non covalent bond (coulombic interaction, hydrogen bonding, π−stacking, ...) and the oxidative process.

Activation of C-H and C-F bonds This project aims at the understanding of the fundamental chemistry involved in the activation of C-H and C-F bonds by transition metal complexes. Selective activation of C-H bonds by metals under mild conditions is a major subject of research, targeting the final functionalization of organic substrates. The characterization of the usually unstable intermediates of the C-H bond activation prior to functionalization is crucial for the mechanistic comprehension of the reaction. It is thus of great importance in organometallic chemistry and catalyst development because it can contribute to deepen our knowledge related to the reactivity of stable bonds and the selective replacement of F atoms.

Articles ºº“Oxygen-Oxygen Bond Formation by the Ru-Hbpp Water Oxidation Catalyst Occurs Solely via an Intramolecular Reaction Pathway” J. Am. Chem. Soc. 2009, 131 (8), 2768-2769 Sophie Romain, Fernando Bozoglian, Xavier Sala, Antoni Llobet ºº“Molecular Catalysts that Oxidize Water to Dioxygen” Angew. Chem. Int. Ed. 2009, 48, 2842-2852 Xavier Sala, Isabel Romero, Montserrat Rodríguez, Lluís Escriche, Antoni Llobet ºº“A Ru-Hbpp-Based Water-Oxidation Catalyst Anchored on Rutile TiO2” ChemSusChem 2009, 2, 321 – 329 Laia Francés, Xavier Sala, Jordi Benet-Buchholz, Lluís Escriche, Antoni Llobet

ºº“Efficient hydrogenation of alkenes using a highly active and reusable immobilized Ru complex on AlPO4” J. Mol. Catal. A: Chem 2009, 308 41–45 Veronica Caballero, Felipa M. Bautista, Juan Manuel Campelo, Diego Luna, Rafael Luque, Jose Maria Marinas, Antonio Angel Romero, Isabel Romero, Montserrat Rodríguez, Isabel Serrano, Jose Miguel Hidalgo, Antoni Llobet ºº“Iron vs. ruthenium—a comparison of the stereoselectivity in catalytic olefin epoxidation” Dalton Trans. 2009, 5910–5923 Jordi Benet-Buchholz, Peter Comba, Antoni Llobet, Stephan Roeser, Prabha Vadivelu, Hubert Wadepohl, Sebastian Wiesner ºº“Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a CuII complex” Dalton Trans. 2009, 6013–6020 Gemma J. Christian, Arnau Arbuse, Xavier Fontrodona, Mª Angeles Martinez, Antoni Llobet, Feliu Maseras

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2. RESEARCH Prof. Llobet Research Group

Articles ºº“Mn(II) complexes containing the polypyridylic chiral ligand (-)-pinene[5,6]bipyridine. Catalysts for oxidation reactions” Dalton Trans, 2009, 8117–8126 Jordi Rich, Montserrat Rodríguez, Isabel Romero, Lydia Vaquer, Xavier Sala, Antoni Llobet, Montserrat Corbella, Marie-Noëlle Collomb, and Xavier Fontrodona ºº“Synthesis and Structure of Novel RuII–N≡C–Me Complexes and their Activity Towards Nitrile Hydrolysis: An Examination of Ligand Effects” Aust. J. Chem. 2009, 62, 1675–1683 J oaquim M ola , D avid P ujol , M ontserrat R odríguez , I sabel Romero,Xavier Sala, Néstor Katz, Teodor Parella, Jordi BenetBuchholz, Xavier Fontrodona, Antoni Llobet ºº“The Ru-Hbpp Water Oxidation Catalyst” J. Am. Chem. Soc. 2009, 131, 15176–15187 Fernando Bozoglian, Sophie Romain, Mehmed Z. Ertem, Tanya K. Todorova, Cristina Sens, Joaquim Mola, Montserrat Rodríguez, Isabel Romero, Jordi Benet-Buchholz, Xavier Fontrodona, Christopher J. Cramer, Laura Gagliardi, Antoni Llobet

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ºº“Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates” J. Am. Chem. Soc. 2009, 131, 16051–1605 Andrea Sartorel, Pere Miró, Enrico Salvadori, Sophie Romain, Mauro Carraro, Gianfranco Scorrano, Marilena Di Valentin, Antoni Llobet, Carles Bo, Marcella Bonchio ºº“DNA-Cleavage Induced by New Macrocyclic Schiff base Dinuclear Cu(I) Complexes Containing Pyridyl Pendant Arms” Inorg. Chem. 2009, 48, 11098–11107 Arnau Arbuse, Marc Font, Mª Ángeles Martínez, Xavier Fontrodona, Mª José Prieto, Virtudes Moreno, Xavier Sala, Antoni Llobet ºº“Oxygen-Oxygen Bond Formation Pathways Promoted by Ruthenium Complexes” Acc. Chem. Res. 2009, 42 (12), 1944–1953 Sophie Romain, Laura Vigara, Antoni Llobet


Dr.

López

RESEARCH GROUP

Group Leader: Núria López Postdoctoral Researchers: Gerard Novell PhD Students: Mónica García / Jaime Gómez / Crisa Vargas Technician: Martín Gumbau Administrative Support: Núria Vendrell

T

can be considered as catalyst candidates for a given chemical transformation. Our collaboration with several experimental groups is of fundamental importance to define and compare models that can later be applied to suggest experiments and new materials to be explored. To this end, the use of massive computational resources, as those

he aim of the group is to employ atomistic simu-

provided by the RES-BSC is required.

lations to understand the mechanisms that gov-

During this year our activities have been centered

ern chemical processes in heterogeneous catalysis.

on: (i) the analysis of selectivity in different process-

Both the analysis of reaction networks, activity and

es, (ii) the study of the links between homogeneous

selectivity issues and the final tests on the stability

and heterogeneous catalysts, i.e. their similarities

of the potential materials are fundamental to es-

and differences for the same catalytic property, and

tablish a solid background to determine when they

(iii) the study of the properties of SnO2-x sensors.

39


2. RESEARCH Prof. López Research Group

The search for new, more active, selective, stable, environmentally friendly and cheaper heterogeneous catalysts has traditionally been performed by means of trial-and-error methods. While a large amount of heuristic knowledge has been achieved, the lack of systematic studies hinders a fast development in an area that is crucial in 90% of the chemical processes performed in industry. Trial-and-error methods are extensive, time consuming and expensive. Although much knowledge has been achieved by the use of experimental techniques, in particular Surface Science, the lack of systematization constitutes a severe problem. In the last 15 years, computational methods have reached the sufficient level of accuracy required for the current chemical problems and enough computational resources are available now. This has boosted a new area of science that can be termed as “Theoretical Heterogeneous Catalysis”. Nowadays, it is possible to obtain accurate models based on atomistic first principles simulations that determine the descriptors controlling the relevant chemical properties. Moreover, atomistic simulations provide a systematic way to evaluate the descriptors in sufficiently large populations of potential catalysts, thus being at the same time a tool for analysis and prediction. The structured knowledge coming from atomistic simulations can shift the present research, which is mainly supported on trial-anderror procedures, to more rationalized methodologies. In this fourth year of activity of the Theoretical Heterogeneous Catalysis group we have concentrated on three main aspects: selectivity, homogeneous-heterogeneous comparisons, and the study of nanowire sensors. Selectivity is a must in the chemical industry. Selective processes reduce the amount of lost material but also diminish the environmental impact of the chemical industries and their energetic costs. The search for selective processes is one of the requirements for the chemical industry in the 21st century. The second research line tries to identify the links between homogeneous and heterogeneous catalysts. Nowadays, research in the field of catalysis is fragmented between two completely independent communities. Surprisingly enough, several processes can be carried out by both kinds of transformations and in addition the same metal is involved. We have compared the second of these transformations (the first one was completed in 2008) by analyzing the chemistry of palladium-containing catalysts to synthesize vinyl acetate (an important monomer in industry). The third research area is devoted to the study of the properties of sensors. Defective tin oxide nanowires can act as gas sensors and thus their electric properties respond to the presence of different gases. In that case, many of the modifications of the signal depend on the gases present in the environment. Thus, stable properties are needed in order to obtain stable devices able to act as sensors and a full control on the phenomena induced by the presence of gases needs to be achieved. Two studies have been devoted to the study analysis of the reactions of hydrocarbons on metal surface. The first one has been done in collaboration with the group of Prof. K. Honkala at the University of Jÿvaskÿla, Finland. Adsorption and conversion of ethylene to ethylidyne on flat (111) and stepped Pd surfaces were studied with the aim to unravel the complex chemistry of small organic molecules on Pd. These processes

40

are crucial to understanding many experimental observations on Pd catalysts involved in selective hydrogenations, steam reforming, polymerization, and several other transformations. Our results provided a view on the complex chemistry of olefins on the surface, where several competitive processes can take place simultaneously, and where a hierarchy among different bond activations was established. For Pd, the C-H bonds of the olefins were found to be the most labile on the surface, followed by C-C and last isomerization processes. From the picture above, the most straightforward reaction mechanism is not always necessarily the one taking place on the surface. Scrambling of H atoms on the organic moieties is the most effective way to generate certain (even long-lasting) isomers on the surfaces. A second work was devoted to the study of the partial hydrogenation of propyne over copper-based catalysts. This work follows the line opened by our contribution in the field in J. Catal. 2007 and was carried out in collaboration with the group of Prof. J. Pérez-Ramírez (ICIQ). Several catalysts were prepared by different state-of-the-art techniques demonstrating that Cu-based catalysts can be as active, selective and resistant as those traditionally employed in the transformation. Under several conditions the new catalysts can even overperform the properties of old ones. In this case, Density Functional Theory based models are employed to understand the reasons behind the high performance found in terms of complete abatement of alkane fractions, see Figure 1. Indeed, the lack of formation of three-dimensional hydride compounds supports the appealing properties found for Cu when compared to Ni or Pd counterparts. In addition, the large degree of dispersion found with the sophisticated techniques employed in the group of Prof. J. Pérez-Ramírez can mitigate oligomerization, one the major drawbacks of these catalysts. Indeed, computational results show that the product distribution can be assigned through Density Functional Theory simulations to the different stability of subsurface phases (carbides, hydrides) and the energetics and barriers for the competing reaction mechanisms. The behavior of Cu in partial alkyne hydrogenation resembles that of Au nanoparticles, whereas Ni is closer to Pd.

Fig 1. Hydrogenation and oligomerization structures for both Cu (red) and Ni (grey) (111) surfaces. Yellow spheres represent C atoms and blue H.

Regarding the links between homogeneous and heterogeneous catalysis, we have compared the production of vinyl acetate by sets of catalysts involving Pd atoms as reaction centres, see Figure 2. We have determined the reaction mechanisms by means of Density Functional Theory applied to molecular models for the homogeneous catalyst and to slabs that model


2. RESEARCH Prof. López Research Group

the most active heterogeneous ensemble in order to unravel the similarities and differences in the reaction networks under these different conditions. We have found that, although the reaction network is similar, the rate-determining step is different. Thus, direct extrapolations from organometallic chemistry to gasphase heterogeneous catalysis should be handled with care.

oxygen vacancy excorporation and healing are confined to the near-surface layer of SnO2-x (bidimensional or near surface diffusion), and completed in short times. Under oxygen-rich conditions, tridimensional diffusion of oxygen vacancies towards the surface takes place at room temperature. In this case, a push-pull mechanism allows bulk-to-surface diffusion and, as a consequence, resistance drifts are longer and the vacancy quenching is more extensive.

Fig 2. Reaction schemes for the synthesis of vinyl acetate with homogeneous and heterogeneous Pd-based catalysts.

Fig 3. Experimental R response as a function of CO presence together with the models showing the perturbation induced by the presence of Ocus atoms. Red spheres stand for O, grey for Sn.

Finally, we have initiated a new research line in the group regarding the properties of sensors. Our work is performed in collaboration with the group of Prof. J. R. Morante at IREC, see Figure 3. Metal oxides present oxygen defects that induce different chemical and physical properties. Experiments performed in SnO2-x sensors show that the dynamics of these vacancies are strongly affected by the presence of different gases in the environment. Experimentally, the electrical resistance of individual metal oxide SnO2-x nanowires shows modulation: when the environment is rich in oxygen, long-term drifts (hours) are observed indicating extended vacancy dynamics. Instead, if CO is present, drifts disappear in minutes. Density Functional Theory indicates that changes in resistance follow the extension of reoxidation. For environments poor in oxygen,

Articles ºº “DFT Study on the Complex Reaction Networks in the Conversion of Ethylene to Ethylidyne on Flat and Stepped Pd” J. Phys. Chem. C 2009, 113, 8278- 8286 J. Andersin, N. López, K. Honkala ºº“Vinyl Acetate Synthesis on Homogeneous and Heterogeneous Pd-Based Catalysts: A Theoretical Analysis on the Reaction Mechanisms” J. Phys. Chem. A 2009, 113, 11758-11762 J. J. Plata, M. García-Mota, A. A. C. Braga N. Lopez, F. Maseras

41


Dr.

Martín

RESEARCH GROUP

Group Leader: Rubén Martín Postdoctoral Researchers: Arkaitz Correa / Paula Álvarez PhD Students: Areli Flores Administrative Support: Ingrid Mateu

mainly focused on the metal-catalyzed, selective ac-

T

We are also interested in the design and implemen-

he major goal in Dr. Martín’s group is to provide solutions to relevant and challenging synthetic

problems from the scientific and industrial standpoint, without losing sight of its environmental impact. In order to meet these challenges, the group is

42

tivation of relatively inert entities of great significance, such as CO2, C-H bonds, C-C bonds and C-O bonds, as these motifs rank amongst the most widespread and fundamental linkages in organic chemistry. tation of metal-catalyzed domino reactions as a high degree of molecular complexity can be achieved in a single step, hence allowing a rapid access to key backbones occurring in many natural products.


2. RESEARCH Prof. Martín Research Group

Activation of inert entities has been and continues to be of extreme interest to any organic chemist. This is especially true with activation of atmospheric molecules such as CO2 or also the activation of relatively inert C-H, C-C or C-O bonds. Certainly, the development of catalytic methods for the activation of the above-mentioned entities would be highly desirable, as many of the current methods involve the use of stochiometric amounts of metal complexes. The research of our group is mainly directed towards the development of novel methodologies for the metal-catalyzed activation of inert entities with the aim of producing synthetically relevant molecules (Figure 1). We are also interested in the mechanism of these reactions, as the understanding of these processes on a fundamental level will in turn lay the foundation for future applications of this chemistry.

Unlike other carboxylation methods using CO2, there is no need for the synthesis of the corresponding organometallic intermediates. In contrast to the well-established carbonylation processes, our protocol does not use highly toxic CO for the preparation of benzoic acids. Furthermore, this method is distinguished by its mild conditions, allowing the tolerance of a wide range of functional groups and substitution patterns. From the methodological point of view, a combined use of experimental and theoretical methods is a key contributory factor to any project´s success. As part of our commitment to the Consolider Ingenio 2010 project (CSD2006-0003), we have started a collaboration with the group of Prof. Maseras in order to understand the factors that influence the mechanism of these reactions from a computational point of view. While certainly preliminar, we have proposed a mechanism in which the crucial step involves a challenging CO2 insertion into the corresponding Pd-C bond (Figure 3).

Fig. 3 – Mechanistic proposal for the Pd-catalyzed carboxylation of aryl halides. Fig. 1 – Research at Martín Laboratories

Pd-catalyzed activation of Carbon Dioxide (CO2) Sustainable development is now accepted by governments, industry and the public as a necessary goal for achieving societal, economic and environmentally objectives. Some of the new challenges for chemists include the discovery and development of new synthetic pathways using renewable sources. In this context, the simplest alternative feedstock is carbon dioxide (CO2). Making chemicals from CO2 would not only conserve petroleum but also reduce CO2 emissions. Moreover, CO2 is nontoxic, abundant, economical and attractive as an environmentally friendly chemical reagent. Our group has launched a program for the synthesis of benzoic acid derivatives from the carboxylation of aryl halides using CO2 as the sole source of carbon (Figure 2)

Pd-catalyzed synthesis of benzocyclobutenones via C-H bond-activation The development of “perfect chemical reactions” that maximize the yield while not generating waste would be highly desirable. In this context, the most promising area of research is the metal-catalyzed C-H bond-functionalization as it allows the elaboration of complex substrates from simple precursors with no waste being generated. In this context, our research group has become interested in the synthesis of benzocyclobutenones via C-H bond-activation protocols. These compounds are key intermediates for the construction of many polycarbocyclic and heterocyclic moieties.

Fig. 4 – Pd-catalyzed C-H bond-activation for the synthesis of benzocyclobutenones.

Fig. 2 – Pd-catalyzed carboxylation of aryl halides with CO2.

The preparation of benzocyclobutenones is usually accomplished by long sequence routes or by using in situ generated benzyne derivatives. Therefore, a direct route to these

43


2. RESEARCH Prof. Martín Research Group

motifs with a diverse and easily manipulated set of substituents would be highly desirable. In this regard, we have recently shown that a very simple process based on a C-H bond-activation protocol provides a direct access to a wide range of functionalized benzocyclobutenones in very high yield (Figure 4).

mechanistically similar to that of benzocyclobutenones. In this case, we propose that the preparation of α-aryl styrenes could follow a pathway based on a 1,4-palladium migration, decarbonylation and a final β-hydride elimination event.

Although in principle several mechanisms are conceivable for the results highlighted in Figure 4, we gathered indirect evidence by studying the cyclization of related compounds and by the measurement of the kinetic isotope effect (kH/kD=2.8). These experiments allowed us to propose a mechanism based on a C-H bond-activation event followed by a challenging reductive elimination step (Figure 5). Fig. 6 – Pd-catalyzed C-H bond-activation for the synthesis of α-aryl styrenes

Future work will be focused on the development of more efficient processes of the topics outlined in 2009. Additionally, we will also study the activation of C-O bonds, a much more challenging task due to its relatively high bond energy. Considering the ubiquity of C-O bonds in nature, it would be highly attractive to develop catalytic methods devoted to the functionalization of these rather unreactive entities to more complex structures.

Fig. 5 – Mechanistic proposal for the Pd-catalyzed synthesis of benzocyclobutenones.

We have also demonstrated that a simple change on the reaction conditions allowed us to prepare α-aryl styrenes in excellent yield with no trace of the corresponding benzocyclobutenone being detected. Interestingly, this reaction could also tolerate a wide range of functional groups, giving access to compounds difficult to access otherwise in essentially one-step operation (Figure 6). While we have not performed yet a comprehensive study, this reaction could potentially be

44

Articles ºº“Metal-catalyzed carboxylation of organometallic reagents with carbon dioxide” Angew. Chem. Int. Ed. 2009, 48, 6201-6204 Correa, A. ; Martin, R. ºº“Palladium-catalyzed direct carboxylation of aryl bromides with carbon dioxide” J. Am. Chem. Soc. 2009, 131, 15974-15975 Correa, A. ; Martin, R.


Prof.

Maseras

RESEARCH GROUP

Group Leader: Feliu Maseras Postdoctoral Researchers: Carina Backtorp / Maria Besora / Ataualpa A. C. Braga / Gemma J. Christian (until

C

omputational chemistry is applied to the study of different chemical processes of

practical interest. DFT and DFT/MM methods are

Jul.) / Steven M. Donald / Sílvia Díez-González (until Sept.)

used to different processes in homogeneous ca-

PhD Students: Torstein Fjermestad / Abel Locati /

talysis, in most cases in collaboration with exper-

Charles Goehry / Chunhui Liu

imental groups. Studies have been carried out on

Visiting Students: Rocío Recio (Sept. – Oct.)

cross-coupling reactions, other C-C bond forma-

Technicians: Martín Gumbau / Joan Iglesias

tion processes, activation of functional groups

Administrative Support: Núria Vendrell

and enantioselective catalysis.

45


2. RESEARCH Prof. Maseras Research Group

Theoretical chemistry has been used as a tool to obtain valuable insight into the mechanism of different reactions. A variety of subjects were studied with the computational tools of density functional theory (DFT) and density functional theory / molecular mechanics (DFT/MM). Most of the applications were in the field of homogenous catalysis.

Palladium-catalyzed C-C cross-coupling Cross-coupling reactions are one of the most used methods for the efficient formation of carbon-carbon bonds in mild conditions. We have focused our efforts this year in the steps of the catalytic cycle different from transmetalation. The oxidative addition step was studied in collaboration with the groups of Prof. Lledós (Bellaterra) and Asensio (Valencia). The stereoselectivity-determining oxidative addition step in the Suzuki-Miyaura cross-coupling of α-bromo sulfoxides was analyzed computationally through DFT calculations on a model system defined by Pd(PMe3)2 and CH3SOCH2Br. Both monophospine and bisphosphine complexes were considered, different reaction pathways being characterized through location of the corresponding transition states. The lowest energy transition states (see Fig. 1) correspond to nucleophilic substitution mechanisms, which imply inversion of configuration at the carbon, in good agreement with experimental data on the process. The energy-lowering and stereodirecting role of the sulfinyl substituent is explained through its attractive interactions with the palladium center, which are only possible in the most favored mechanisms.

cis-[PdMe2(PPh3)2] in the presence of additives reveals that: (1) There is no universal coupling mechanism. (2) The coupling mechanism calculated for cis-[PdMe2(PMe3)2] is direct, but PPh3 retards the coupling for cis-[PdMe2(PPh3)2], and DFT calculations support a switch of the coupling mechanism to dissociative for PPh3. (3) Additives that would provide intermediates with coupling activation energies higher than a dissociative mechanism (e.g., common olefins) produce no effect on coupling. (4) Olefins with electron-withdrawing substituents facilitate the coupling through cis-[PdMe2(PR3)(olefin)] intermediates with much lower activation energies than the starting complex or a tricoordinated intermediate.

Other reactions for C-C bond formation Cross-coupling is a widely used method for C-C bond formation, but not the only possible one. The field of organocatalysis was explored in a collaboration with the group of Prof. Coelho (Campinas, Brazil). A MoritaBaylis-Hillman (MBH) reaction catalyzed by thiourea was monitored by the experimental group by ESI-MS(/MS) and key intermediates were intercepted and characterized. These intermediates suggest that thiourea acts as an organocatalyst in all steps of the MBH reaction cycle, including the rate-limiting proton-transfer step. DFT calculations in our group, performed for a model MBH reaction between formaldehyde and acrolein with trimethylamine as base and in the presence or the absence of thiourea, prove that thiourea accelerates MBH reactions by decreasing the transition state energies through bidentate hydrogen bonding throughout the whole catalytic cycle. In the rate-limiting proton-transfer step (see transition state in Fig. 2), the thiourea acts not as a proton shuttle, but as a Brønsted acid stabilizing the basic oxygen center that is formed in the process.

Fig. 1 – Key transition state in the oxidative addition of an a-bromosulfoxide to a palladium bisphospine comlex.

Reductive elimination was analyzed in collaboration with the groups of Prof. Lledós (Bellaterra), Espinet (Valladolid) and de Lera (Vigo). A DFT study of R-R reductive elimination (R: Me, Ph, vinyl) in plausible intermediates of Pd-catalyzed processes was carried out. These include the square-planar tetracoordinated systems cis-[PdR2(PMe3)2] themselves, possible intermediates cis-[PdR2(PMe3)L] formed in solution or upon addition of coupling promoters (L: acetonitrile, ethylene, maleic anhydride –ma–), and tricoordinated intermediates cis-[PdR2(PMe3)] (represented as L: empty). The activation energy ranges from 0.6 to 28.6 kcal/mol in the gas phase, increasing in the order vinylvinyl < Ph-Ph < Me-Me, depending on R, and ma < “empty” < ethylene < PMe3 MeCN, depending on L. Comparison of the calculated energies with experimental data for the coupling of

46

Fig. 2 - Key transition state in the Morita-Baylis-Hillman reaction between formaldehyde and acrolein with trimethylamine as base and thiourea as catalyst. Selected distances are given in A. (Color code for atoms: carbon, black; nitrogen, blue; oxygen, red; sulfur, yellow; fluor, green; hydrogen, grey)

Activation of functional groups Transition metal compounds often allow selective functional group activation. Mechanistic knowledge is fundamental for modulation of this reactivity and design of more efficient processes. The activation of haloalkanes was studied in collaboration with the group of Prof Pérez (Huelva). Carbon−halogen (C−X) bonds (X = Cl, Br) can be easily functionalized with ethyl diazoacetate (N2CHCO2Et) in the presence of silver-based catalysts containing the TpxAg core (Tpx = hydrotrispyrazolylborate ligand). Poly-


2. RESEARCH Prof. Maseras Research Group

halomethanes are converted into products derived from the formal insertion of the carbene CHCO2Et units into the C−X bond. In the case of monohaloalkanes (C4−C6), cleavage of the C−X bond is observed, with formation of XCH2CO2Et and the corresponding olefin. Experimental evidence and theoretical calculations have led to the proposal of a novel mechanism to account for these transformations, in which the metal participates along the pathway in all the reaction steps. Among the experimental data, the first example of a metal-induced, asymmetric functionalization of a C−Cl bond by carbene insertion is included (ee = 14 ± 2%). The dehydrogenation of an amine group was studied in collaboration with the group of Prof. Llobet (ICIQ). The spontaneous oxidation of an amine group to an imine has been observed experimentally in an octa-aza macrocyclic dinucleating ligand LH4 coordinated to CuII. The reaction is bimolecular and spontaneous in which amine groups of one macrocycle are oxidised and the CuII centres of a second macrocyclic complex are reduced. No additional oxidating or external base agents are required. DFT calculations are carried out to compare the reaction with that recently reported for a ligand coordinated to an FeIII centre, but which requires an external base as proton acceptor. The computational results show that the copper and iron catalysed amine to imine reactions proceed via different mechanisms.

Enantioselective catalysis Rhodium-catalyzed asymmetric hydrogenation was analyzed in collaboration with the group of Prof Vidal-Ferran (ICIQ). DFT and DFT/MM calculations were carried out on the rate-determining step of the addition of dihydrogen to methyl-(N)acetylaminoacrylate catalyzed by a rhodium catalyst containing a bidentate phosphine-phosphinite ligand. DFT calculations reproduce the experimental results, while DFT/MM calculations do not. The failure of DFT/MM methods for this particular problem was analyzed through a series of calculations with different partitions between the DFT and MM regions, which show that electronic effects of all ligand substituents considered are critical. The analysis of these electronic effects provides key information on the role of each of the substituents in the outcome of the overall catalytic process. The mechanistic and regiochemical aspects in the Au(I)-catalyzed intermolecular hydroalkoxylation of allenes were also studied computationally. The most favorable pathway is nucleophilic attack of an Au(I)-coordinated allene, which occurs irreversibly. An Au(I)-catalyzed mechanism was proposed that allows the facile interconversion of regioisomeric allylic ether products. The regioisomers are connected via a stabilized diether intermediate with a C−Au σ-bond, which successfully explains the observed regioselectivity for the thermodynamic product.

Fig. 3 - Dehydrogenation from amine to imine in the coordination sphere of a copper complex

Articles ºº“Mechanism of the [(NHC)AuI ]-Catalyzed Rearrangement of Allylic Acetates. A DFT study”; Org. Lett. 2009, 11, 81-84 C. Gourlaouen, N. Marion, S. P. Nolan, F. Maseras ºº“Structural Analysis of Zincocenes with Substituted Cyclopentadienyl Rings” Chem. Eur. J. 2009, 15, 924-935 R. Fernández, A. Grirrane, I. Resa, A. Rodríguez, E. Carmona, E. Alvarez, E. Gutiérrez-Puebla, A. Monge, J. M. López del Amo, H.-H. Limbach, A. Lledós, F. Maseras, D. del Río

ºº“C-C Coupling Constants, 1 JCC , are Reliable Probes for -C-C Agostic Structures”

Organometallics 2009, 28, 940-943 C. Boulho, T. Keys, Y. Coppel, L. Vendier, M. Etienne, A. Locati, F. Bessac, F. Maseras, D. A. Pantazis, J. E. McGrady ºº“Agostic interactions in alkyl derivatives of sterically hindered tris(pyrazolyl)borate complexes of niobium”

Coord. Chem. Rev. 2009, 253, 635-646 M. Etienne, J. E. McGrady, F. Maseras

47


2. RESEARCH Prof. Maseras Research Group

Articles ºº“The C-C Reductive Elimination in Palladium Complexes, and the Role of Coupling Additives. A DFT Study Supported by Experiment.” J. Am. Chem. Soc. 2009, 131, 3650-3657 M. Pérez-Rodríguez, A. A. C. Braga, M. Garcia-Melchor, M. H. Pérez-Temprano, J. A. Casares, G. Ujaque, A. R. de Lera, R. Álvarez, F. Maseras, P. Espinet ºº“Protonation of Transition Metal Hydrrides: A Not So Simple Process” Chem. Soc. Rev. 2009, 38, 957-966 M. Besora, A. Lledós, F. Maseras ºº “The Role of Amide Ligands in the Stabilization of Pd(II) Tricoordinated Complexes. Is the Pd-NR2 Bond Order Single or Higher?” Theor. Chem. Acc. 2009, 123, 75-84 S. Moncho, G. Ujaque, P. Espinet, F. Maseras, A. Lledós ºº“Gold(I)-Catalyzed Intermolecular Hydroalkoxylation of Allenes: a DFT study” Org. Lett. 2009, 11, 2237-2240 R. S. Paton, F. Maseras ºº“Why is the Suzuki-Miyaura cross-coupling of sp3 carbons in a-bromosulfoxide systems fast and stereoselective? A DFT study on the mechanism” J. Org. Chem. 2009, 74, 4049-4054 C. Gourlaouen, G. Ujaque, A. Lledós, M. Medio-Simon,G.Asensio, F. Maseras ºº“Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a CuII complex” Dalton Trans. 2009, 6013-6020 G. J. Christian, A. Arbuse, X. Fontrodona, M. A. Martinez, A.Llobet, F. Maseras

48

ºº“A DFT/MM analysis of the effect of ligand substituents on asymmetric hydrogenation catalyzed by rhodium complexes with phosphine-phosphinite ligands” Can. J. Chem. 2009, 87, 1273-1279 S. M. A. Donald, A. Vidal-Ferran, F. Maseras ºº“The Mechanism of the Catalytic Functionalization of Haloalkanes by Carbene Insertion: An Experimental and Theoretical Study” Organometallics 2009, 28, 5968-5981 J. Urbano, A. A. C. Braga, F. Maseras, E. Alvarez, M. M. Díaz-Requejo, P. J. Pérez ºº“Vinyl acetate synthesis on homogeneous and heterogeneous Pd-based catalysts: a theoretical analysis on the reaction mechanisms” J. Phys. Chem. A 2009, 113, 11758-11762 J.J. Plata, M. García-Mota, A. A. C. Braga, N. López, F. Maseras ºº“Brønsted Acid-Catalyzed Morita-Baylis-Hillman Reaction: A New Mechanistic View for Thioureas Revealed by ESI-MS(/ MS) Monitoring and DFT Calculations” Chem. Eur. J. 2009, 15, 12460-12469 G. W. Amarante, M. Benassi, H. M. S. Milagre, A. A. C. Braga, F. Maseras, M. N. Eberlin, F. Coelho ºº“The Nature of M-B Versus M=B Bonds in Cationic Terminal Borylene Complexes: Structure and Energy Analysis in Borylene Complexes [(h 5-C 5H 5)(CO) 2MB(h 5C 5 Me 5 )] + , [(h 5 -C 5 H 5 )(CO) 2 M(BMes)] + and [(h 5 -C 5 H 5 ) (CO)2M(BNMe2)]+ (M= Fe, Ru,Os)” Organometallics 2009, 28, 6442-6449 K. K. Pandey, A. Lledós, F. Maseras


Prof.

Melchiorre RESEARCH GROUP

Group Leader: Paolo Melchiorre PhD Students: Sandra Alcoberro / Giulia Bergonzini / Carlo Cassani Administrative Support: Agustina Gisbert

man health, i.e. new bioactive compounds for the benefit of society. Overall, our research is guided by the premise that investing in fundamental research into advanced

T

synthetic chemistry is key to future advances in oth-

ple) to find cost-effective and sustainable synthetic

ity profiles thus enabling previously inaccessible

he main aim of our group is to exploit the potential of asymmetric organocatalysis (which

involves only organic elements in the active princimethods that can streamline the synthesis of complex, chiral compounds that may be relevant to hu-

er scientific domains, such as biomedical research. We want to innovate around novel reactivity concepts, which may induce unconventional reactivtransformations.

49


2. RESEARCH Prof. Melchiorre Research Group

Targeting Structural and Stereochemical Complexity by Asymmetric Organocatalysis Finding cost-effective and highly stereoselective ways to reproduce the rich structural diversity and complexity of natural molecules has always represented a formidable synthetic challenge for chemists, especially in relation to the study of biologically active compounds. Indeed, many drugs used today are natural products or natural-product derivatives. Enantioselective catalysis is one of the most efficient chemical approaches to target the challenging issue associated with structural and stereochemical complexity, because this is the only rational means of producing useful chiral compounds with high optical purity in an economical, energysaving and environmentally benign way.

Chiral Primary Amine-catalyzed Cascade Reactions While chiral secondary amines have proven invaluable for the asymmetric functionalization of aldehydes, primary amine catalysis offers the unique possibility of participating in processes between sterically-demanding partners, providing a practical solution to the issue of activating α,β-unsaturated ketones toward a well defined enamine-iminium tandem sequence. We recently developed a series of organocascade approaches that affords straightforward access to a range of formal DielsAlder adducts, having three or four stereogenic centers, with very high optical purity (Figure 2). Importantly, catalyst 1 - a chiral primary amine directly derived from natural cinchona alkaloids - efficiently activates acyclic enones while selectively directing the reaction manifold toward a stepwise doubleMichael addition sequence instead of a pericyclic path. This method furnishes a complementary approach to the venerable Diels-Alder reaction for the one-step synthesis of complex cyclohexane scaffolds with excellent optical purity.

Fig. 1 - The concept of iminium-enamine activation in Tandem sequence

Recently, the potential of asymmetric catalysis has been expanded by the introduction of simple chiral small molecules as highly efficient catalysts of many transformations. One of the most powerful organocatalytic strategies is organocascade catalysis. It exploits the ability of chiral amines to efficiently combine two modes of catalyst activation of carbonyl compounds (iminium and enamine catalysis) into one mechanism, thereby allowing the rapid conversion of simple achiral starting materials into stereochemically complex products having multiple stereocentres and very high optical purity (Figure 1). This one-step strategy requires neither time-consuming, costly protection/deprotection nor isolation procedures of intermediates. We want to innovate around the development of novel organocascade strategies for rapidly synthesize complex compounds embodying features of natural molecules. Since the vast majority of natural products and drug-like compounds possess heterocyclic moieties, we will focus on preparing diverse heterocyclic compounds, such as spirocyclic oxindole derivatives. We recognized as a necessary step the identification of novel reactivity concepts to enable the inclusion of unprecedented transformations into elaborate yet experimentally simple organocascade reactions.

50

Fig. 2 - Organocascade with enones promoted by chiral primary amine 1: enamine-iminium activation for a double-Michael sequence

The versatility of chiral primary amine catalyst 1 can be further exploited to solve the longstanding issue associated with the aminocatalytic activation of α,β-disubstituted enals. The use of 1 allows including this challenging substrates class into iminiumenamine cascade sequences that lead to valuable precursors of α-amino acids having two adjacent stereogenic centers, one of which is quaternary, with very high enantiomeric purity (Figure 3).

Fig. 3 - Organocascade catalysis with α,β-disubstituted enals: olefin arylamination and thio-amination strategies

High Complexity Made Easy We recently developed distinct cascade reactions that utilize two chiral amines, each activating different carbonyl compounds, toward well established domino sequences. The


2. RESEARCH Prof. Melchiorre Research Group

processes lead to the direct, one-pot synthesis of complex spirocyclic oxindoles having three or four stereogenic carbon atoms with extraordinary level of stereocontrol and starting from simple precursors. Despite the spiro-oxindole core features in a number of natural products as well as medicinally relevant compounds, its stereocontrolled synthesis, particularly installing the challenging spiro-quaternary stereocentre, pose a great synthetic problem. Only a few venerable asymmetric transformations, such as cycloaddition processes or the intramolecular Heck reaction, have proven suitable for achieving this challenging goal. The described complementary approaches demonstrate the potential of organocascade catalysis to face challenging synthetic problems using disparate tactics (Figure 4).

Articles ºº “Organocascade reactions of enones catalyzed by a chiral primary amine” Angew. Chem. Int. Ed. 2009, 48, 7196-7199 L.-Y. Wu, G. Bencivenni, M. Mancinelli, A. Mazzanti, G. Bartoli, P. Melchiorre ºº“Asymmetric organocatalytic cascade reactions with α-substituted α,β-unsaturated aldehydes” Angew. Chem. Int. Ed. 2009, 48, 7892-7894 P. Galzerano, F. Pesciaioli, A. Mazzanti, G. Bartoli, P. Melchiorre ºº“Targeting structural and stereochemical complexity by organocascade catalysis: construction of spirocyclic oxindoles having multiple stereocentres” Angew. Chem. Int. Ed. 2009, 48, 7200-7203 G. Bencivenni, L.-Y. Wu, A. Mazzanti, B. Giannichi, F. Pesciaioli, M.-P. Song, G. Bartoli, P. Melchiorre

Prof. Melchiorre joined ICIQ in September, 2009.

Fig. 4 - Complementary organocascade strategies for achieving molecular complexity. Chiral primary amine A selectively activates ketones toward a tandem domino reaction, exploiting an enamine – iminium activation sequence. Chiral secondary amine B promotes a triple organocascade by way of an enamine – iminium – enamine activation of aldehydes

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Prof.

Muñiz

RESEARCH GROUP

Group Leader: Kilian Muñiz Postdoctoral Researchers: Álvaro Iglesias PhD Students: Anton Lishchynskyi / Cesar Ríos Visiting Professor: Edwin G. Pérez Administrative Support: Rita Rahme

O

ur laboratory is currently interested in all aspects of activation and transformation of nitrogen

compounds at transition metal sites. This includes activation of N-N and N-H bonds, chemical transformation of metal-amide complexes and their application for amide transfer to C-C bonds.

We are particularly interested in developing protocols for transition-metal catalysed direct diamination of alkenes. To accomplish this goal, the group develops entirely new synthetic tools such as palladium(IV) catalysis and studies the underlying mechanistic details.

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2. RESEARCH Prof. Muñiz Research Group

Catalysis with its inherent beneficial economical and environmental features is a core technology for the 21st century. Its power to realise previously impossible transformations renders it the ideal approach to address the demands of modern synthesis of valuable intermediates and building blocks. Nitrogen containing molecules are key players in a variety of compounds of biological, medicinal and pharmaceutical interest. Central to our research interest is the development of new catalytic diamination and amidation reactions with a particular focus on oxidation catalysis. Over the past years, we have succeeded in the development of a series of new transformations including the first example of an osmium-catalysed ketamination reaction and a platinumcatalysed aminoalkoxylation under aerobic conditions.

addition, the reaction offers a unique entry for the construction of bisindolines, bipyrrolidines and related nitrogen heterocycles of interest. The observation that palladium in high oxidation state is a prerequisite for the successful catalytic realization of alkylnitrogen groups led us to consider these transformations in a broader context. Current understanding of this process suggests the involvement of an SN2-type transition state in the C-N bond formation (Figure 2), where the reduction of the palladium metal centre represents the driving force for the overall process.

A strong emphasis of our present research is on metal-catalysed diamination of alkenes, an elusive oxidative transformation in organic synthesis. The importance of such a reaction stems from the ubiquitous application of vicinal diamines in a variety of important fields. Initial exploration in this area employed tethered ureas as nitrogen sources under intramolecular reaction control (Figure 1). The reaction employs simple palladium(II) salts as catalysts and iodosobenzene diacetate as terminal oxidant. It makes use of a palladium(IV) catalyst state for the crucial step of carbon-nitrogen bond formation.

Fig. 2 – Pd(IV) Catalysis for C-N Bond Formation.

Obviously, such a sequence holds great promise for the design of general palladium catalysis for alkyl-nitrogen bond forming events. Future research at ICIQ will realise such reactivity.

Fig. 1 – Representative Examples of Intramolecular Diamination of Alkenes

The current state of the art in Pd(IV)-catalysed diamination of alkenes is represented by the successful intramolecular diamination of stilbenes and related compounds, which employs sulfonamides as nitrogen sources. The reaction is characterised by a remarkable flexibility of the palladium catalyst, which promotes both aminopalladation and final C-N bond instalment with complete selectivity and under mild conditions. In

Articles ºº“High-Oxidation State Palladium Catalysis: New Reactivity for Organic Synthesis” Angew. Chem. Int. Ed. 2009, 48, 9412 K. Muñiz

Prof. Muñiz joined ICIQ in November, 2009.

53


Prof.

Palomares RESEARCH GROUP

Group Leader: Emilio Palomares Postdoctoral Researchers: Eugenia Martínez / John Noel Clifford PhD Students: Miquel Planells / Anna Reynal / Antonio Sánchez / Margherita Bolognesi / James William Ryan / Ivan Castelló / Josep Albero Technician: Amparo Forneli Visiting Students: Xavier González (Jul. – Aug.) / Volkan Altunay (Jul. – Sept.) / Joan Vidal (Jul.) / Luis Lanzetta and Marc Cayuela (Jul.) / Manuel Lloris (Nov.) Administrative Support: Eva Busto

R

esearch on carbon neutral renewable energy sources based upon the combination of su-

pramolecular chemistry, nanostructured inorganic materials science and optoelectronic device physics is emerging as a powerful technology platform for the 21st Century. Since the formation of the group in

2006, our main interest has been the development of light driven molecular devices where the limited functionalities of individual molecules are enhanced by their organisation into larger heterosupramolecular systems, which can be used to convert light into different types of energy sources. Furthermore, we are involved in the development and study of new hybrid devices for light-emitting applications.

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2. RESEARCH Prof. Palomares Research Group

Fig. 1 – Charge versus voltage characteristic for two different Ruthenium complexes (AR20 and N719) in the presence of citric acid.

Building upon our experience in the study of interfacial charge transfer processes at the molecular level, recent investigations have paid particular attention to the control of the charge recombination processes that limit the performance of molecular photovoltaic devices. For example, we investigated the effect of additives on the electrolyte of Dye Sensitised Solar Cells (DSSC). We demonstrated that nanoscale control of electron transfer reactions between photo-injected electrons and the oxidised electrolyte in the device under illumination is possible by the interaction between the additives and the molecular sensitizer (Figure 1). In this case, the functionality achieved represents a significant advance in understanding one of the processes that limits the efficiencies of these new photovoltaic devices. These studies clearly demonstrate the ability of our group to design, fabricate and characterise such innovative systems. Furthermore, within the framework of a European project (FP7-ROBUST DSSC-212792), we also established that it is possible to combine different dyes at the surface of transparent mesoporous nanocrystalline semiconductor films to achieve panchromatic sensitisation, which improves further the device photoresponse. This work combines the use of organic dyes that absorb light in different regions of the solar spectrum. In particular, polythiophene based dyes and phthalocyanines were utilized for the light harvesting at the near IR part of the solar spectrum. We carried out extensive work on these intensely absorbing near IR dyes leading to deeper insights into structure-device efficiency relationship. Moreover, we found that such aromatic systems absorbing light at low energies have in several cases a negative effect on the device efficiency. In fact, we have confirmed that in the case of Zinc based phthalocyanines, the electron injection process does not limit the device performance. Since 2006, the group has been working on the characterisation of the supramolecular interactions between the organic sensitizers and the species at the electrolyte in order to: (a) achieve higher efficiencies in DSSC and (b) study the role of the peripheral moieties in the dyes (Figure 2). This work is one of the objectives to be developed within the Ministerio de Educación y Ciencia project (CTQ-2007-60746: Estudio de molecu-

las óptica y electroquímicamente activas y su aplicación en dispositivos fotovoltaicos moleculares). The results have indeed been very promising and we have hitherto obtained photovoltaic devices that showed slow recombination dynamics for the e--TiO2/electrolyte+ reaction when using supramolecular binding units for Lithium (Figure 2).

Fig. 2 – Differences in charge density versus voltage for two perylene dyes. Notice that the upper sensitizers have a lithium coordination unit.

Furthermore, the studies focusing on the dye molecular structure-device efficiency relationship showed that there is an important influence of the substituent moieties at the bipyridine rings that affects dramatically the cell photovoltage and photocurrent. Further work has also been carried out during the framework of the European Network of Excellence (FP6OrgaPVNet) where Prof. Palomares is the national representative. The network, that coordinates more than 10 European countries (www.orgapvnet.eu), is the European platform for future projects for the development of molecular photovoltaic technology. In line with the formation of research clusters on molecular photovoltaics, in 2008 the project HOPE was awarded by the MICINN within the CONSOLIDER-INGENIO 2010 program. The HOPE project coordinates 13 research groups working on the development of molecular solar cells and light emitting displays.

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2. RESEARCH Prof. Palomares Research Group

The work carried out in our group has attracted the attention of several national and international companies working in the area of renewable energy. For example, ACCIONA SOLAR has signed contracts with the ICIQ for the study and development of this new technology. Furthermore, other companies such as CETEMMSA have established contacts with ICIQ to expand the fundamental knowledge on the processing of organic materials in flexible substrates. Moreover, Prof. Palomares leads a Strategic Project that focuses on the applications of molecular photovoltaic devices. The project, FOTOMOL (www.fotomol.org), combines the interest from the Spanish industry leaders in solar energy: ACCIONA, ATERSA and ISOFOTON and 5 different research centres. Our group has also focused on the development of low-cost/ easy to use environmental molecular and biomolecular probes. In 2008 we developed a sensor based on our previous work on colorimetric determination of mercury(II) using Ruthenium bis-thiocyanate molecules. We demonstrated that different diastereoisomers of Ruthenium receptors have different behaviour when mercury ions are present in aqueous solutions. During 2009 we have finalized our work on the development of a multi-variable analytical system to study the absorption changes upon mercury addition to the molecular chemodosimeter. Finally, the group has continued the research in HYLEDS (Hybrid Light Emitting Devices) where the use of a metal oxide as the electron injection layer avoids the use of highly reactant metals as counter-electrodes. We are able to prepare such devices which are stable in air and so do not need the expensive encapsulating process essential to LEDs and OLEDs. We have optimized the deposition processes and thickness of the different materials involved, as well as the scalability of the active area in order to prepare devices with commercial interest. The collaboration with CETEMMSA about indoor lighting applications has led to the creation of devices with 1 cm2 of active area (Figure 3). On the other hand, the optimization of the deposition technique has allowed the preparation of devices of 0.9 and 1 cm2 with efficiencies close to those reported in the literature for 0.01cm2 devices.

Articles ºº“Mercury optical fiber probe based on a modified cladding of sensitized Al2O3 nano-particles.” Sensors Actuat., B-Chem. 2009, 143(1), 103-110. Perez-Hernandez, Javier; Albero, Josep; Llobet, Eduard; Correig, Xavier; Matias, Ignacio R.; Arregui, Francisco J.; Palomares, Emilio. ºº“Photo-induced electron recombination dynamics in CdSe/ P3HT hybrid heterojunctions.” Phys. Chem. Chem. Phys. 2009, 11(42), 9644-9647. Albero, Josep; Martinez-Ferrero, Eugenia; Ajuria, Jon; Waldauf, Christoph; Pacios, Roberto; Palomares, Emilio. ºº“Supramolecular interactions in dye-sensitised solar cells.” J. Mater. Chem. 2009, 19(32), 5818-5825. Planells, Miquel; Cespedes-Guirao, F. Javier; Goncalves, Luis; Sastre-Santos, Angela; Fernandez-Lazaro, Fernando; Palomares, Emilio. ºº “Charge recombination studies in conformally coated trifluoroacetate/TiO2 modified dye sensitized solar cells (DSSC).” J. Mater. Chem. 2009, 19(30), 5381-5387. Sanchez-Diaz, Antonio; Martinez-Ferrero, Eugenia; Palomares, Emilio. ºº“Extended π-aromatic systems for energy conversion: phthalocyanines and porphyrins in molecular solar cells.” J. Porphyr. Phthalocya. 2009, 13(4-5), 645-651. Rio, Yannick; Vazquez, Purificacion; Palomares, Emilio. ºº“Ru(II)-phthalocyanine sensitized solar cells: the influence of co-adsorbents upon interfacial electron transfer kinetics.” J. Mat. Chem. 2009, 19(28), 5016-5026. Morandeira, Ana; Lopez-Duarte, Ismael; O’Regan, Brian; MartinezDiaz, M. Victoria; Forneli, Amparo; Palomares, Emilio; Torres, Tomas; Durrant, James R. ºº“Electron transfer dynamics in dye-sensitized solar cells utilizing oligothienylvinylene derivatives as organic sensitizers.” ChemSusChem 2009, 2(4), 344-349. Clifford, John N.; Forneli, Amparo; Lopez-Arroyo, Leticia; Caballero, Ruben; de la Cruz, Pilar; Langa, Fernando; Palomares, Emilio. ºº“The XXI challenge: cheap and renewable energy sources.” ChemSusChem 2009, 2(4), 267-8. Palomares, Emilio ºº“Structure-Function Relationships in Unsymmetrical Zinc Phthalocyanines for Dye-Sensitized Solar Cells.” Chem. Eur. J. 2009, 15(20), 5130-5137. Cid, Juan-Jose; Garcia-Iglesias, Miguel; Yum, Jun-Ho; Forneli, Amparo; Albero, Josep; Martinez-Ferrero, Eugenia; Vazquez, Purificacion; Graetzel, Michael; Nazeeruddin, Mohammad K.; Palomares, Emilio; Torres, Tomas. ºº “Diastereoselectivity and molecular recognition of mercury(II) ions.” Inorg. Chem. Commun. 2009, 12(2), 131-134. Reynal, Anna; Albero, Josep; Vidal-Ferran, Anton; Palomares, Emilio.

Fig. 3 – Device of 1 cm2 prepared at ICIQ at work.

56

ºº“Multivariate calibration analysis of colorimetric mercury sensing using a molecular probe.” Anal. Chim. Acta 2009, 633(2), 173-180. Perez-Hernandez, Javier; Albero, Josep; Correig, Xavier; Llobet, Eduard; Palomares, Emilio.


Prof.

Pérez-Ramírez RESEARCH GROUP

Group Leader: Javier Pérez-Ramírez Scientific Group Coordinator: Sònia Abelló Postdoctoral Researchers: Adriana Bonilla / Mªdel Rosario Caicedo / Laura Durán / Sharon Mitchell PhD Students: Amol Amrute / Blaise Bridier / Georgiana Stoica / Danny Verboekend Laboratory Engineer: Marta Santiago Visiting Students: Michel André Chabaneix (May. – Aug.) Administrative Support: Beatriz Martín

T

he mission of our group covers the development of heterogeneous catalysts, multifunctional ma-

terials, and reactor engineering concepts devoted to sustainable eco-efficient technologies that guaranty intensified processes, improved exploitation of feedstocks and natural resources, reduction of energy usage, and minimized environmental impact. Bridging the intrinsic gaps of time and length for the rational design of catalytic processes is attempted

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2. RESEARCH Prof. Pérez-Ramírez Research Group

under the umbrella of Catalysis Engineering, integrating microlevel (catalyst), mesolevel (reactor), and macrolevel (process). The nature of our research is mostly application-oriented, motivating tight links to industry. These collaborations are balanced by curiosity-driven projects of fundamental nature. Four main areas can be distinguished: (i) design of hierarchical porous zeolites, (ii) development of new catalysts for specific applications, and (iii) advanced methodologies for mechanistic and kinetic investigations.

Hierarchical porous zeolites Our group is recognized for pioneering work in the design of hierarchical porous zeolites by selective silicon extraction, referred to as desilication or base leaching. Hierarchical zeolites integrate the original microporosity and a secondary mesopore network. Consequently, the access and intracrystalline transport of molecules to/from the active sites is improved, enhancing their effectiveness as catalysts. We have demonstrated that the lattice trivalent cation, Al3+, Ga3+, Fe3+, and B3+, regulates the alkalineassisted hydrolysis of silicon towards mesoporosity development. This finding implies that the desilication treatment can be generalized to multiple framework compositions.

Silicon dissolution in TPAOH was much slower than in NaOH, making the demetallation process highly controllable. Following this approach, a novel desilication variant involving NaOH treatment of ZSM-5 in the presence of quaternary ammonium cations has been developed. The organic cation (TPA+ or TBA+) acts as a pore-growth moderator in the crystal by OH--assisted silicon extraction, largely protecting the zeolite crystal during the demetallation process. Other novel methods to desilicate zeolites include the application of microwave radiation during alkaline treatment of ZSM-5 or the use of NaAlO2 followed by HCl washing. Microwaves greatly accelerate the development of intracrystalline mesoporosity compared to the standard treatment (conventional heating). In the two-step route, the contact of the zeolite with NaAlO2 solutions induced mild leaching of framework silicon. However, the porosity of the resulting samples was mostly blocked by NaAlO2-derived deposits and Si-containing debris. A subsequent acid washing with HCl or oxalic acid removed the blocking species, largely regaining the native microporosity and further uncovering the extensive intracrystalline mesoporosity generated in the first step. Strong focus is kept on the rational design of hierarchically structured zeolites. The porous superiority of such systems has been ascribed to numerous factors as for example increased mesoporous surface area and mesopore volume. In our recent work, we have put forward that the optimal design of these materials is attained through the maximization of the hierarchy factor (HF), that is, by enhancing the mesopore surface area without a severe penalization of the micropore volume. This parameter is a powerful tool to categorize hierarchical zeolite families obtained by different synthetic methods, and can be used to relate functions of hierarchical materials, e.g. transport, adsorption properties, and overall catalytic performance.

Fig. 1 – Front-covers highlighting our work on the partial detemplation-desilication approach over beta zeolite (left) and the pore-growth moderation by tetraalkylammonium hydroxides (right).

Different strategies have been pursued to synthesize and characterize novel hierarchical zeolites, and to assess their accessibility, diffusion, adsorption and catalytic performance aspects. For example, partial detemplation of zeolites followed by desilication in alkaline medium is demonstrated as a powerful and elegant approach to design hierarchical zeolites with tailored degree of mesoporosity. Based on the fact that the template-containing zeolite is virtually inert to Si leaching upon treatment in alkaline medium, the partial removal of the structure-directing agent creates regions in the crystal susceptible to mesopore formation by subsequent desilication, while template-containing regions are protected from silicon extraction. Hierarchical zeolites have been also prepared by desilication in aqueous solutions of tetraalkyl-ammonium hydroxides.

58

Fig. 2 – The hierarchy factor (HF) plotted as a function of the relative mesopore surface area and the relative micropore volume of different zeolite types prepared by different methods.

We have also defined the Accessibility Index (ACI) as a tool to quantify and standardize acid site accessibility in zeolites and to rank the effectiveness of synthetic strategies to prepare hierarchical zeolites. The desilication treatment has been conducted over other zeolite frameworks, including ferrierite, ITQ-4, and ZSM-22, aiming at higher efficiency of the material in catalytic reactions. The optimization of the treatment conditions (NaOH concentration, temperature, and time) was required to intro-


2. RESEARCH Prof. Pérez-Ramírez Research Group

duce substantial mesoporosity without significantly altering the micropore structure due to excessive Si leaching.

ration with Dr. López, both Cu-Al and previously reported Ni-Al hydrotalcites-based systems in partial hydrogenation from an experimental and theoretical approach. Based on that, we have designed a new family of ternary Cu-Ni-Fe catalysts with appropriate metal ratios displaying 100% propene selectivity in partial propyne hydrogenation. In order to enhance our fundamental understanding, we are currently investigating the effect of CO as selectivity enhancer over Pd and other metal-based catalysts.

Temporal Analysis of Products

Fig. 3 – Desilication over ITQ-4.

Compared to other frameworks (MFI, MTW, MOR, and BEA), mesopore formation by desilication in ferrierite requires harsher conditions likely due to the high stability of framework Al. The typical morphology of the ZSM-22 crystal needle-like agglomerates also requires severe desilication conditions to yield significant mesoporosity. Along with porosity modification, significant changes in composition, structure, and acidity occurred upon desilication of ITQ-4. Relationships have been established between the physico-chemical properties of the zeolites and their characteristics in the adsorption and elution of light hydrocarbons (C2-C5, alkanes and alkenes) as well as in the catalytic activity in LDPE pyrolysis. Biocatalyst development continues to be of great industrial interest due to the high achievable activities and selectivities. Preliminary work has demonstrated that lipase enzymes supported in zeolitic based materials are catalytic active and show improved reusability with respect to their purely siliceous counterparts, due to the increased strength of electrostatic interactions. The dependence of activity on factors such as the identity of the lipase enzyme and on the properties of the support materials (porosity, acidity, surface functionalization) has been assessed. Increasing the porosity of commercial microporous zeolites by desilication, results in an increased capacity for the incorporation of guest species. In combination with organic functionalization, this has been successfully exploited to permit controllable variation in the size of the resulting mesopores.

Partial alkyne hydrogenation Reducing the level of highly unsaturated compounds in olefinic streams is required to fulfil the stringent specifications for both chemical and polymer-grade chemical. Since 2006, we have been developing new catalysts and providing fundamental understanding of the partial hydrogenation of alkynes. Continuing in the development of non-noble metal catalysts using the hydrotalcite route, Cu3Al, usually regarded as a poorly active catalyst, has proved to be highly active, selective, and displaying stable performance in partial propyne hydrogenation after proper activation. We have described and compared, in collabo-

The Temporal Analysis of Products (TAP) reactor is a time-resolved transient pulse technique that provides valuable mechanistic and kinetic understanding of adsorption, diffusion, and reaction in gas-solid systems. We are currently investigating the mechanism of HCl oxidation to Cl2, known as Deacon process, which is an environmentally benign, economic and industrially relevant reaction. This process has been studied over RuO2-based catalysts in bulk and supported forms. Transient studies in the TAP reactor led to an improved mechanistic understanding of this complex and experimentally demanding reaction over practical catalysts. The extrapolation to copperbased catalysts is underway.

Fig. 4 – Transient mechanistic study of the gas-phase HCl oxidation to Cl2 catalysts.

Catalysis by Activated Dawsonites The chemistry of synthetic dawsonites is not fully understood, and their application in heterogeneous catalysis has been so far scarcely investigated. Following the investigation line in our group, the potential of as-synthesized (as ?) and activated dawsonites in catalysis has been evaluated. Thermally activated Na-dawsonite is efficient or even more active for the green dimethyl carbonate production by transesterification of ethylene carbonate with methanol than basic reference catalysts in the state-of-the-art. Besides, the catalysts can be successfully recycled for several consecutive runs, and the activity is kept when the reaction is scaled-up.

Fig. 5 – Activated Al and Ga-dawsonites are active catalysts for the epoxidation of cyclooctene.

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2. RESEARCH Prof. Pérez-Ramírez Research Group

Dawsonite materials containing Ga have been for the first time synthesized by our group, and they are promising catalysts for the redox epoxidation of alkenes. Thermally decomposed Gadawsonite is the best transition-metal-free catalyst reported so far for the epoxidation of cyclooctene with hydrogen peroxide. We have demonstrated the potential of dawsonitetype compounds as precursors of basic and redox catalysts.

Environmental catalysis The implementation of N2O abatement technology in flue-gases of fluidized-bed combustors (FBC) should likely occur within the next few years due to (i) the significant emission, even exceeding that of chemical production processes, (ii) the enforcement of environmental regulations by governments, and (iii) the recent inclusion of N2O as a tradable greenhouse gas under the EU Emission Trading Scheme. The extrapolation of commercial catalysts for N2O abatement in chemical plants to stationary combustion sources such as fluidized-bed combustions requires careful consideration. In spite of their remark-

able performance for process-gas N2O abatement in nitric acid plants, mixed oxide catalysts such as spinel, perovskite, and hexaaluminate, lack chemical stability and experience severe deactivation under FBC conditions, mainly due to the presence of SO2 and H2O. We have demonstrated that steam-activated FeZSM-5 zeolite displays remarkable activity and stability and is a serious candidate for practical implementation in stationary combustion facilities. We have discovered the positive effect of SO2 on the N2O decomposition over iron-containing zeolites. SO2 promotes the rate of N2O decomposition more efficiently than other reducing agents (NH3) and promoters (NO). The effect of SO2 as selective reductant is independent of the framework type and composition, preparation method, and iron content, suggesting that its occurrence is not determined by a highly specific iron speciation. The eventual formation of sulfate-type species on the zeolite surface during the N2O+SO2 reaction and its potential role in the catalytic process is currently evaluated by means of operando spectroscopic investigations.

Articles ºº“Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication” Adv. Funct. Mater. 2009, 19, 164-172 J. Pérez-Ramírez, S. Abelló, A. Bonilla, J. C. Groen ºº“Mechanism of ammonia oxidation over PGM (Pt, Pd, Rh) wires by temporal analysis of products and density functional theory” J. Catal. 2009, 261, 217-223 J. Pérez-Ramírez, E.V. Kondratenko, G. Novell-Leruth, J.M. Ricart

60

ºº“Theoretical investigation of the inversion parameter in Co3-SAlSO4 (s=0-3) spinel structures” Solid State Ionics 2009, 180, 1011-1016 F. Tielens, M. Calatayud, R. Franco, J.M. Recio, J. Pérez-Ramírez, C. Minot ºº“Desilication of ferrierite zeolite for porosity generation and improved effectiveness in polyethylene pyrolysis” J. Catal. 2009, 265, 170-180 A. Bonilla, D. Baudouin, J. Pérez-Ramírez

ºº“Mesoporous metallosilicate zeolites by desilication: On the generic pore-inducing role of framework trivalent heteroatoms” Mater. Lett. 2009, 63, 1037-1040 J.C. Groen, R. Caicedo-Realpe, S. Abelló, J. Pérez-Ramírez

ºº“Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching” Appl. Catal. A 2009, 364, 191-198 S. Abelló, A. Bonilla, J. Pérez-Ramírez

ºº“Accelerated generation of intracrystalline mesoporosity in zeolites by microwave-mediated desilication” Phys. Chem. Chem. Phys. 2009, 11, 2959-2963 S. Abelló, J. Pérez-Ramírez

ºº“Na-dawsonite derived aluminates for DMC production by transesterification of ethylene carbonate” Appl. Catal. A 2009, 365, 252-260 G. Stoica, S. Abelló, J. Pérez-Ramírez

ºº“Quantification of enhanced acid site accessibility in hierarchical zeolites - The accessibility index” J. Catal. 2009, 264, 11-14 F. Thibault-Starzyk, I. Stan, S. Abelló, A. Bonilla, K. Thomas, C. Fernandez, J.-P. Gilson, J. Pérez-Ramírez

ºº“Mesoporous ZSM-5 zeolites prepared by a two-step route comprising sodium aluminate and acid treatments” Microporous Mesoporous Mater. 2009, 128, 91-100 R. Caicedo-Realpe, J. Pérez-Ramírez

ºº“Synthesis of dimethyl carbonate by transesterification of ethylene carbonate over activated dawsonites” ChemSusChem 2009, 301-304 G. Stoica, S. Abelló, J. Pérez-Ramírez

ºº“Epoxidation catalysts derived from aluminum and gallium dawsonites” Appl. Catal. A 2009, 371, 43-53 G. Stoica, M. Santiago, P.A. Jacobs, J. Pérez-Ramírez, P.P. Pescarmona

ºº“Evaluation of catalysts for N2O abatement in fluidized-bed combustion” Appl. Catal. B 2009, 90, 83-88 M. Santiago, M.A.G. Hevia, J. Pérez-Ramírez

ºº“Zeolite Catalysts with Tunable Hierarchy Factor by PoreGrowth Moderators” Adv. Funct. Mater. 2009, 19, 3972-3979 J. Pérez-Ramírez, D. Verboekend, A. Bonilla, S. Abelló


Prof.

Pericàs

RESEARCH GROUP

Group Leader: Miquel À. Pericàs Senior Researcher: Ciril Jimeno Project Coordinator (CONSOLIDER): Sonia Sayalero Postdoctoral Researchers: Carles Rodríguez / Rafael Martín / Diana Almasi / Sarabindu Roy (until Jun.) / Moumita Roy (until Jun.) PhD Students: Rocío Marcos / Ester Alza / Carolina Mendoza / Pinar Kasaplar / Erhan Özkal / Laura Osorio / Xacobe Couso (until Jul.) / Francesc Xavier Caldentey (until Jul.) Technicians: Patricia Llanes / Míriam Sau Visiting Students: Julien Rolland (Feb. – May.) Administrative Support: Mercè Mateu / Núria Mas

T

he main interests of the research group of Miquel A. Pericàs are enantioselective catalysis

and nanotechnology. More specifically, attention is paid to pluridisciplinary aspects common to these two areas. This research has the generic goals of the development of new immobilized catalytic systems to perform the enantioselective formation of C-C and C-X bonds through procedures with improved sustainability characteristics and the development of nanomaterials with application in the fields of catalysis, selective detoxification and biomedicine. The following research lines are active in

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2. RESEARCH Prof. Pericàs Research Group

the group: a) Synthesis of modular ligands for enantioselective catalysis; b) Anchoring of catalytic ligands on polymers; c) Development of multipurpose, functional metal nanoparticles; d) Understanding catalytic processes through mechanistic studies; e) Development of flow systems for the continuous production of enantiopure materials through catalytic processes.

The main topics covered during 2009 consisted on the development of new homogeneous and immobilized catalytic systems that allow the enantioselective formation of carboncarbon bonds through procedures with improved sustainability characteristics. Both ligands for metal-catalyzed reactions and organocatalysts have been designed, prepared and immobilized on polystyrene-based organic polymers. The ultimate methodological goal of implementing single-pass, continuous flow organometallic and organocatalized processes mediated by polymer-supported catalysts developed by the research group, has been achieved.

Synthesis of modular ligands for enantioselective catalysis The research line on ligand design was initiated in the group several years ago. It stems from the idea that ideal ligands for catalytic processes can be efficiently prepared by modular construction from purely synthetic, yet enantiopure precursors.

Throughout the last year this line proved fruitful, rendering three papers on different applications. New bis(oxazoline) ligands (BOXs) containing biaryl substitutents at the C-4 position and H or CH2OR substituents at the C-5 position have been synthesized using Suzuki cross-coupling as the main tool for structural diversity. Copper, zinc, and palladium complexes of the prepared BOXs have been evaluated in the following catalytic asymmetric processes: Acylation with kinetic resolution of trans-1,2-cyclohexanediol (Cu), enantioselective Friedel–Crafts alkylation of indole (Zn), and enantioselective alkylation of 3-acetoxy-1,3-diphenylpropene (Pd). In collaboration with the group of Anton Vidal-Ferran, a family of enantiopure diphenylphosphinooxazolines (PHOX) containing in their structures a sterically tunable alkoxymethyl group (-CH2OR) has been optimized for the palladium-catalyzed asymmetric allylic amination. The optimal catalyst (R=CH 3), depicting very high catalytic activity and broad scope applicability, has been further modified to include an ω-alkynyloxy substituent of variable length for polymer supporting via click chemistry, and has been anchored onto slightly cross-linked azidomethyl polystyrene. The length of a polymethylene chain connecting the PHOX unit with the 1,2,3-triazole linker has been optimized, and the first polymer-supported PHOX ligands for the highly enantioselective allylic amination have been prepared in this manner. Conditions for catalyst recovery and reuse in microwave-promoted amination reactions have been established, and the system has been finally adapted to continuous flow operation.

Enantiopure epoxides, available in both enantiomeric forms through a variety of well-established procedures (Sharpless, Jacobsen and Shi epoxidations, to name the most successful) were identified as the ideal starting point for our quest. Our research in this field is based on the mechanistic understanding of the processes under study as the main guide of the ligand optimization process. Thus, both experimental techniques such as kinetics and detection of intermediates, and high-level theoretical calculations are employed to gather information on the reactions and to assist the design of new ligands.

Fig. 2 – Continuous flow system used in allylic amination reactions with polymer-supported PHOX ligands

Supported catalysts and flow processes One of the long-term goals in our research group is the development of polymer-supported catalytic ligands to promote stereoselective reactions in a more efficient manner. The advantages of the covalent immobilization of these catalysts onto a polymeric support are clear: avoiding the need for separation of the catalyst and the product, simplified work-up procedures and, in the most favourable cases, the possibility of implementing a continuous flow process. Fig. 1 – Suzuki strategy for the synthesis of biaryl containing amino alcohols and bis(oxazolines)

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A very important aspect of this research is the development of new methods for immobilizing ligands and catalysts


2. RESEARCH Prof. Pericàs Research Group

onto solid suports. In this respect, a new tris(1-benzyl-1H1,2,3-triazol-4-yl)methanol ligand has been prepared by a triple Cu(I)-catalyzed alkyne−azide 1,3-dipolar cycloaddition (CuAAC). This ligand forms a stable complex with CuCl, which catalyzes the Huisgen 1,3-dipolar cycloaddition on water or under neat conditions. Low catalyst loadings, short reaction times at room temperature, and compatibility with free amino groups make this complex an outstanding catalyst for CuAAC. In particular, this new catalytic species shows a very high efficiency in CuAAC reactions where the reactants have a polymeric nature. Application of metal complexes of analogs of this ligand to a variety of catalytic processes is currently underway in our laboratories.

Polymer-supported proline-type organocatalysts have now been tested in asymmetric Mannich reaction of aldehydes with preformed N-(p-methoxyphenyl)ethyl glyoxylate imine. The results replicate those recorded with the same catalyst set for aldol reactions in water, thus confirming the beneficial effect of the 1,2,3-triazole linker connecting proline with the polymeric backbone which turns out to be crucial for catalytic activity and enantioselectivity. The robustness of the catalyst is illustrated by the successful implementation of a continuous flow process for aldehydes involving reaction times of only 6.0 minutes.

An internacional patent entitled “Tris (1,2,3-triazol-4-yl) organometallic compounds as catalysts and processes using them” has been presented (S. Özçubukçu, E. Ozkal, C. Jimeno, M. A. Pericàs, PCT Appl. File Number EP09382121, 2009).

Fig. 5 – Schematic representation of the continuous-flow system used in asymmetric Mannich reaction.

Also in the field of polymer-supported ligands for stereoselective catalysis, our group has been long involved in the preparation and anchoring of amino alcohols used to promote the addition of organozinc reagents to aldehydes. For instance, a modified version of a very successful ligand developed in our group was prepared, in which enantiopure triphenylethylene oxide was opened with piperazine instead of morpholine. This allowed using the second nitrogen as an anchoring point to link the monomer to a Merrifield resin. Fig. 3 – A highly active catalyst for Huisgen 1,3-dipolar cycloadditions based on the tris(triazolyl)methanol-Cu(I) structure

Special attention is paid in the laboratory to the development of anchoring strategies that do not affect in a negative manner the catalytic activity of the supported monomers or, in the ideal case, that even induce an improvement of their catalytic performance. In this context, we have developed a polystyrenesupported version of enantiopure (S)-α,α-diphenylprolinol trimethylsilyl ether. Very interestingly, this resin displays catalytic activity and enantioselectivity comparable to the best homogeneous catalyst in the Michael addition of aldehydes to nitroolefins. Furthermore, it represents the first example of an insoluble catalyst successfully dealing with aldehydes in water. In addition, this catalyst exhibits unprecedented substrate selectivity that allows, in practice, inducing the completely selective reaction of a linear short-chain aldehyde in the presence of its α-branched regioisomer or a ketone.

Fig. 4 – Chemoselective Michael addition of butanal to β-nitrostyrene catalyzed by polystyrene-supported (S)-α,α-diphenylprolinol trimethylsilyl ether.

Fig. 6 – Continuous-flow enantioselective arylation of aldehydes.

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2. RESEARCH Prof. Pericàs Research Group

Noteworthy, this catalytic resin has allowed the development of the first catalytic enantioselective arylation of aldehydes employing an insoluble catalyst, and has been used as the basis for a single-pass, continuous flow highly enantioselective ethylation of aldehydes characterized by very short residence times (down to 2.8 minutes). According to these precedents, we considered that this solid-supported amino alcohol could be a good candidate for a planned continuous enantioselective production of diarylmethanols.

Gratifyingly, the desired aryl propanols were obtained in high conversions and enantioselectivities in a single-pass process, thus avoiding the need to recirculate the reagents’ solution to achieve good results. A variety of aldehydes could be effectively submitted to this procedure with excellent results in all cases.

Articles ºº“A highly selective, polymer-supported organocatalyst for Michael additions with enzyme-like behavior” Adv. Synth. Catal. 2009, 351, 3051-3056 Alza, E.; Pericàs, M. A.

ºº“Towards Continuous Flow, Highly Enantioselective Allylic Amination: Ligand Design, Optimization and Supporting” Adv. Synth. Catal. 2009, 351, 1539-1556 Popa, D.; Marcos, R.; Sayalero, S.; Vidal-Ferran, A.; Pericàs, M. A.

ºº“Continuous flow enantioselective arylation of aldehydes with ArZnEt using triarylboroxins as the ultimate source of aryl groups” Beilstein J. Org. Chem. 2009, 5, 56 Rolland J.; Cambeiro X. C; Rodriguez-Escrich C.; Pericàs M. A.

ºº“Amino thiols versus amino alcohols in the asymmetric alkynylzinc addition to aldehydes” Tetrahedron: Asymmetry 2009, 20(12), 1413-1418 Subirats, S.; Jimeno, C.; Pericàs, M. A.

ºº“A Solid-Supported Organocatalyst for Highly Stereoselective, Batch, and Continuous-Flow Mannich Reactions” Chem. Eur. J. 2009, 15, 10167-10172 Alza, E.; Rodríguez-Escrich, C.; Sayalero, S.; Bastero, A.; Pericàs, M. A. ºº“A Highly Active Catalyst for Huisgen 1,3-Dipolar Cycloadditions Based on the Tris(triazolyl)methanol−Cu(I) Structure” Org. Lett. 2009, 11, 4680-4683 Ozçubukçu, S.; Ozkal, E.; Jimeno, C.; Pericàs, M. A. ºº“Synthesis of highly modular bis(oxazoline) ligands by Suzuki cross-coupling and evaluation as catalytic ligands” Tetrahedron 2009, 65, 8199-8205 Cattoën, X.; Pericàs, M. A.

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ºº“Functionalized nanoparticles as catalysts for enantioselective processes” Org. Biomol. Chem. 2009, 7(13), 2669-2677 Roy, S.; Pericàs, M. A. ºº“Di-platinum complexes containing thiolato-urea ligands: structural and anion binding studies” Dalton Trans. 2009, 16, 2974-2985 Mendoza, C.; Benet-Buchholz J.; Pericàs, M. A; Vilar, R.


Prof.

van Leeuwen RESEARCH GROUP

Group Leader: Piet W.N.M. van Leeuwen Scientific Group Coordinator: Zoraida Freixa (until Nov.) Postdoctoral Researchers: Henrik Gulyás (until Jul.) / Mathieu Tschan / Nicolas Clément / Yvette Mata (until Sept.) / Marta Giménez (until Sept.) / Thomas Pullmann / Olivier Jacquet / David González PhD Students: Mª Dolores Segarra / Sergio Ponsico / Cornelia Peña (Dec.) / David Max Rivillo (until Mar.) Technician: Josep Maria López Visiting Students: Norbert Geels (May. – Jun.) / Emanuele Amadio (Feb. – Apr.) / Sara Artola (Summer Fellow, Jul. – Sep.) Administrative Support: Marta Moya

T

he main research interest of the group is the development of new and more efficient cata-

lytic systems via a thorough study of ligand effects in homogeneous catalysis. Our research strategy is based essentially on ligand design and a judicious combination of classic synthetic methodologies and modern combinatorial and supramolecular approaches for a fast generation of diverse catalytic entities. Libraries of ligands with diverse properties (such as bite angle, sterics or electronics) based on trial and error have been pursued by many investigators, but

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2. RESEARCH Prof. van Leeuwen Research Group

our approach concerns analysis and rationalization of the catalytic performance aiming at a better understanding of the catalytic systems as the real milestone using molecular modelling and operando spectroscopy.

The development of wide bite angle diphosphines is one of the areas of expertise of the group. A representative example is the well known ligand Xantphos, possessing a natural bite angle close to 110º (Scheme 1). Due to its unusual bite angle, it showed outstanding catalytic performance in many processes which coined it as a privileged ligand for homogeneous catalysis. Initially designed for hydroformylation and hydrocyanation, it is now mostly applied in palladium cross coupling catalysis. More than 1100 structures are known in literature based on Xantphos-like ligands. The success of Xantphos evidenced the importance of the bite angle, and, led by van Leeuwen’s group, it activated the study of this key ligand parameter for chelating ligands. In 2003 another unusual ligand was synthesized in van Leeuwen’s group, viz. SPANphos. Initial studies pointed to a preferred bite angle of around 180º, making it into a trans ligand. Moreover, the ligand is chiral due to its spiro centre.

Scheme 2: Chiral Nitrogen and Phosphorus-based SPAN Ligands.

Ligands Stabilizing Dinuclear Species It was found that SPANphos stabilizes selectively dinuclear complexes, which are of interest as dinuclear catalysts. Examples of such ligands are scarce, even more so quiral ones. Dinuclear species of SPANphos showed outstanding performance in the rhodium-catalyzed carbonylation of methanol. It is the most active catalyst known so far. In recent years, we designed and synthesized several new ligands, (more rigid than SPANphos), that form solely dinuclear species (López, Scheme 3) containing two bridging halide anions. The rhodium dimers formed with these ligands are slightly more active than dinuclear SPANphos complexes.

Scheme 3: Diphosphines forming exclusively dinuclear complexes.

Scheme 1: Xantphos and SPANphos diphosphines.

The stepwise mechanism is being studied (collaboration with Haynes, Sheffield). The rhodium(III) bisacetyl tetraiodide or triiodide-chloride dimers, products of a migration step after oxidative addition, have been isolated and characterized (see Figure 1).

Covalent approaches SPANphos and derivatives The initial range of SPAN-diphosphines developed in Amsterdam (Freixa, Beentjes) was extended at ICIQ by Jiménez, Roca, and Sala, and a deeper understanding of the ligand’s conformational diversity was gained in collaboration with Bo and Benet-Buchholz. The backbone turned out to be more flexible than simple MM2 calculation had suggested and even cis complexes can be obtained when the other ligands impose such a structure. Since 2007, the spiro-bischroman skeleton has been used to construct a library of chiral diamines, diimines and phosphinoamine ligands (Sala, García, Jacquet, Clément, Scheme 2). The potential catalytic applications of such ligands both in transition metal catalysis and organocatalysis were studied together with Claver as part of the Consolider-Ingenio 2010 project (Jacquet). The enantiomeric mixtures of all compounds were successfully separated enabling us to study the ligands in asymmetric catalysis. SPANamine catalyzes enantioselective fluorination of β-keto-esters, as a ligand with nickel and palladium, and surprisingly also as an “organic” catalyst in the absence of a metal. The ee’s obtained equal the best ones from literature for this reaction.

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Fig. 1: Dinuclear acetylrhodium intermediate.

Bulky monophosphines New ligands of intermediate bulkiness related to the above ones were developed in a project sponsored by Dow Chemical (Tschan). They are used for the selective telomerization of 1,3-butadiene with methanol, a process that came on stream in Tarragona in 2008 for the synthesis of 1-octene applied in the production of LLDPE. In the palladium catalyzed reaction the new ligands, see for example Scheme 4 (patent submitted), gave a higher conversion and selectivity to 1-methoxyocta2,7-diene, while the catalyst is also much more stable than the one presently being used. A window for electronic and steric


2. RESEARCH Prof. van Leeuwen Research Group

properties has been established for ligands that give good results under industrial conditions. Another patent with new structures has been submitted.

Two ditopic ligands coordinated to titanium(IV) leave two coordination sites open for the coordination of two alkoxides (or a dialkoxide). It was envisaged that the use of chiral diols might produce catalysts that can be used as enantio-selective catalysts, e.g. in rhodium catalyzed hydrogenation. An example of such a structure is shown in Scheme 5.

Scheme 4: New ligands for butadiene telomerization.

Supramolecular approaches Supramolecular interactions are frequently used nowadays as an alternative to covalent bonding for the construction of catalytic systems. In our work, supramolecular interactions are used for the construction of the ligand backbone. A Metal as a Template Ditopic ligands that contain both a hard ligand and a soft ligand were used (Rivillo). The hard ligand is an anionic bidentate used to connect two ditopic ligands with a hard assembly metal, such as zinc or titanium. This leads to a much stronger assembly than those based on Lewis acid/base interactions. The soft ligands remaining, phosphorus ligands so far, form a bidentate that can be used for the soft metal to be used in catalysis. The properties of the bidentate diphosphine are determined by the coordination properties of the assembly metal and the hard ligand parts. This strategy enabled us to generate a large number of ligands with different properties (as for instance the P–P distance and P–M–P angle) by changing the assembly metal (see Figure 2). This project benefits from a modular construction of the basic set of monophosphines via the use of a Schiff base condensation to assemble the building blocks.

Scheme 5: A remote chiral inducer for enantioselective hydrogenation.

The catalysts were prepared by in situ mixing of all components and in a rapid screening up to 80% ee was obtained for methyl 2-acetamido-3-phenylacrylate. In view of the remote position of the chiral inducer, this first result is very promising. Metal salphens as templates The aim of this project is the use of oligo-metal salphen molecules as templates for ditopic or oligo-topic ligands (Ponsico). When the number of connectors on each part is different, supramolecular aggregates will form in a controlled manner (e.g. three bidentates will combine with two platforms having three acceptors each (Vernier assemblies). To obtain more stable entities, ionic bonding is employed. A simple example synthesized is shown in Scheme 6, in which the three zinc atoms will coordinate two carboxylates carrying a phosphine, thus forming a diphosphine. The ligand was used for the synthesis of several complexes and in rhodium catalyzed hydroformylation.

Molecular modeling predicted that the structures shown in Figure 2 would lead to diphosphines with preferred bite angles of ~110°, although the systems are highly flexible. Indeed, both cis

Scheme 6: An oligosalphen template and an ionic phosphine carboxylate.

A trypticene-based backbone is shown in Figure 3 (collaboration with MachLachlan, Vancouver). Fig 2: Diphosphines generated by a combinatorial approach.

and trans transition metal complexes were obtained (Pd, Pt, Rh) depending on the preference of the metal complex used. In rhodium catalyzed hydroformylation several ligands gave high selectivity to linear aldehyde formation, typical of wide bite angle diphosphines; the assemblies always performed better than the monodentate ditopic ligands. Catalysts prepared in situ using hetero-mixtures of ditopic ligands gave different results from those of the homo-combinations, several of which indeed being better as we learnt by trial and error. In spite of the strong zinc-anion binding, rapid exchange of ditopic ligands takes place, forming the non-statistical hetero-mixtures. As a result mixing isolated complexes or in situ mixing of components gave the same results in catalysis.

Figure 3: Diphosphines generated by Lewis interactions.

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2. RESEARCH Prof. van Leeuwen Research Group

Hydrogen Bonding Secondary phosphine oxides (SPO) associate effectively via hydrogen bonding to give an anionic ligand system, with properties close to those of phosphines. The new chiral binaphthyl SPO which gave active rhodium hydrogen transfer catalysts, was used as a ligand in platinum complexes. They are active as nitrile hydration catalysts and for the first time kinetic resolution of dinitriles was accomplished to chiral amide-nitrile products. Tunable phosphines Phosphines containing azobenzene groups were successfully switched between cis and trans isomers, both in free ligands and in their platinum complexes (Segarra). Unfortunately no effect in catalysis could be observed (Pd allylation, Rh hydroformylation). A switchable dipyridine ligand was synthesized which combines the structure of the previously studied diphosphinine trans ligand (collaboration with Müller, Eindhoven) and the azo switch function (Scheme 7).

Figure 4: Trans diphosphinines generated by hydrogen bonding interactions.

We embarked on the synthesis of supramolecular variants of trans ligating diphosphinines aiming at a more flexible bridge than that of the phenyl coupled one (with Müller, Eindhoven). The building blocks (containing phenylgroups in ortho and para positions, not shown in Figure 4) were successfully synthesized.

Articles

Scheme 7: Switchable dipyridine ligand.

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ºº“Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions” Chem. Soc. Rev. 2009, 38, 1099–1118. M.-N. Birkholz; Z. Freixa; P. W. N. M. van Leeuwen.


Prof.

Vidal

RESEARCH GROUP

Group Leader: Anton Vidal Postdoctoral Researchers: Dana Popa (until Feb.) / Elisenda Reixach / Ian J. Munslow (until Nov.) / Anne-Sophie Felten / Armen Panossian / Amilan J. Devadoss / Pablo Etayo / Steven Donald (joint collaboration with Dr. Maseras group until Aug.)

PhD Students: Helmut Degenbeck / José Luis Núñez / Ignacio Mon Laboratory Coordinator: Héctor Fernández (from Sept.) Visiting Students: Felix Rudolphi (Feb. – May.) / Álex de la Fuente (Summer Fellow Jul. – Sept.) Administrative Support: Paula Segovia

O

ur current research aims mainly encompass the design, preparation and application of efficient

and reliable catalytic asymmetric methodology. A modular design of the catalysts, the versatility of the synthetic strategies and the computational analysis of the catalytic event are key factors in our strategy.

The group is particularly interested in asymmetric catalysis, and our current aims encompass the design, preparation and application of new catalytic systems. Despite the remarkable progress in the development of asymmetric catalysts, this field still represents an exciting, and never-ending challenge

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2. RESEARCH Prof. Vidal Research Group

for chemists. Criteria such as stereoselectivity, chemoselectivity, turnover number enhancements, rate, robustness, or recoverability are always amenable to improvement. Two factors have contributed to the remarkable progress in the field. First and foremost, the use of ligands derived from enantiopure non-natural starting materials has broadened the structural diversity of available catalysts. Secondly, the modular nature of the ligands has facilitated the tuning of their performance by modifying the stereoelectronic properties of the different molecular fragments (modules). A reduced group of ligands, the so called “Priviliged Chiral Catalysts”, have gained prominence through their ability to effect a wide variety of unrelated transformations under very high enantiocontrol and in high yield. The research group is pursuing two objectives in the field of asymmetric catalysis. In the first instance, it is aimed to develop new ligands with the potential, a priori at least, to be applied to several transformations of interest (Priviliged Chiral Catalysts). Secondly, we are developing a strategy to generate a set of supramolecular ligands which resemble a privileged structure yet at the same time offer a range of closely geometrically related active sites. A library of new P-OP ligands (phosphine-phosphinites 1 and phosphine-phosphites 2), easily available in two synthetic steps from enantiopure Sharpless epoxy-ethers, has been prepared. Epoxide ring-opening with nucleophilic trivalent phosphorus derivatives has allowed the introduction of the phosphine functionality in the chiral skeleton and further derivatisation of the corresponding hydroxy phosphines with trivalent phosphorus electrophiles have rendered a library of P-OP ligands 1 and 2 (Figure 1).

Fig. 1 – P-OP Ligands

Fig. 2 – “Lead” P-OP Ligand in Rh-mediated Asymmetric Hydrogenation

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The modular design of our P-OP ligands „„ Allows to incorporate up to six molecular fragments. „„ Allows to modify the stereoelectronics of the phosphorus functionalities. „„ Allows to control the stereogenic centres between the phosphorus groups. A library of highly modular P-OP ligands has been prepared and their use in rhodium-mediated asymmetric hydrogenation has been assessed. The “lead” ligand of the series (Figure 2) has shown to have outstanding catalytic properties in the rhodium catalysed asymmetric hydrogenation of a wide variety of functionalised alkenes. The remarkably good performance and modular nature of the catalyst makes it attractive for future applications. The strategy utilised to discover new chiral catalysts -tuning of the performance of the catalyst by modifying the stereoelectronic properties of the molecular fragments or modules- is based on a correct hypothesis. The results described show that the different parts of a given chiral catalyst can be optimised separately, so that it is possible to achieve high levels of enantioselectivity even when starting from a mediocre ligand. Computational studies have revealed the main influence of the different molecular fragments (modules) of the lead catalyst on the stereochemical outcome of the reaction: the highly achieved selectivity is a result of a combined action between the chiral-BINOL-phosphite moiety and ligand backbone chirality. Work is in progress to discover new catalysts for asymmetric hydrogenation in still challenging fields (C=N, unfunctionalised C=C bonds and aromatic compounds). Catalysis has been one of the longstanding proposed applications of supramolecular chemistry, which has reached a level of development that allows the practitioner to achieve the design and construction of complex multicomponent assemblies with exquisite detail. Efficient supramolecular systems capable of recognition and catalysis have emerged in recent years, however, the application of supramolecular interactions to generate chiral catalysts is still in its infancy, and reports in the literature are scarce. Our group is interested in the gen-


2. RESEARCH Prof. Vidal Research Group

eration of chiral ligands capable of exploiting supramolecular interactions, and is based on a self-assembly process between the chiral and catalytic components. During the self-assembly process, the chiral information will be transferred from the chiral unit to the catalytic unit and a new supramolecular entity will be formed which will assume the role of the ligand in the asymmetric transformation. Hydrogen bonding has long been used as a driving force for chiral recognition and binding. A thermodynamically controlled resolution driven by the formation of hydrogen bonds has allowed for the generation of diastereomerically enriched com-

plexes, by chirality transfer from an enantiopure building block to a dynamically racemic biaryl derivative. A switchable sense of induction could be achieved depending on the substituents of the chiral block. Our work shows the potential of non-covalent interactions [hydrogen bond and π(CH)] for transmission and control of chirality at the molecular level: a chirally oriented conformation can be created not only by stereogenic elements of a chiral inducer, but also by additional supramolecular interactions which are capable of reversing the sense of induction. Work is in progress to exploit this strategy in the preparation of chiral ligands for asymmetric transformations of interest.

Fig. 3 – Control of chirality driven by supramolecular interactions

Articles ºº “Diasteroselectivity and Molecular Recognition of Mercury(II) Ions” Inorg. Chem. Commun. 2009, 12, 131-134 A. Reynal, J. Albero, A. Vidal-Ferran, E. Palomares º º“Towards Continuous Flow, Highly Enantioselective Allylic Amination: Ligand Design, Optimization and Supporting” Adv. Synth. Catal. 2009, 351, 1539-1556 D. Popa, R. Marcos, S. Sayalero, A. Vidal-Ferran, M.A. Pericàs

ºº“A DFT/MM Analysis of the Effect of Ligand Substituents on Asymmetric Hydrogenation Catalyzed by Rhodium Complexes with Phosphine-Phosphinite Ligands” Can. J. Chem. 2009, 87, 1273-1279 S.M.A. Donald, A. Vidal-Ferran, F. Maseras ºº “Supramolecular-Directed Chiral Induction in Biaryl Derivatives” J. Org. Chem. 2009, 74, 8794-8797 J. Etxebarria, H. Degenbeck, A.-S. Felten, S. Serres, N. Nieto, A. Vidal-Ferran

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2. RESEARCH Research Support Area

2.2 Research Support Area

Area Manager: Dr. Lluís Solà (Dr. Gisela Colet, Oct. 2009) Administrative support: Eva Casco The Research Support Area provides the scientific instrumentation needed by the researchers from the various groups and by the technology platforms developed at the institute. The area is organized in different Units, each one comprising one or several related techniques, or, alternatively, comprising a group of techniques used by a particular research discipline. The Area started its activities at the same time as the research groups in 2004, with five units: Nuclear Magnetic Resonance, X-ray Diffraction, High Resolution Mass Spectrometry, Parallel Synthesis & Process Chemistry, and General Instrumentation. Altogether these Units had the basic equipment to cover the initial needs of the research carried out at the institute. In the following years, the Area grew in response to the researchers needs, incorporating additional equipment and techniques, and creating new Units. In this respect, in 2006, the Area incorporated the Heterogeneous Catalysis Unit, which has instrumentation for studying gas phase reactions catalyzed by solids, and the Photophysics Unit, which has instrumentation for characterizing light induced physicochemical processes. In July 2009 and as a split of the General Instrumentation Unit, it was created the Spectroscopic and Kinetics Unit, that gives scientific support in terms of different spectroscopic techniques and in the study of reaction mechanisms focusing on

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reaction rate measurements. Then, the General Instrumentation Unit became the Chromatography, Thermal Analysis and Electrochemistry Unit with reference to the techniques treated. Moreover, also in 2009, the former Parallel Synthesis & Process Chemistry Unit incorporated the microflow reactors belonging to the Marie Curie Unit led by Prof. van Leeuwen and became what we now call the Chemical Reaction Technologies Unit. In 2009, the area comprised the following 8 units: „„ Nuclear Magnetic Resonance „„ X-Ray Diffraction „„ High Resolution Mass Spectrometry „„ Chemical Reaction Technologies „„ Chromatography, Thermal Analysis and Electrochemistry „„ Heterogeneous Catalysis „„ Photophysics „„ Spectroscopic and Kinetics Specialized technicians ensure the maintenance and correct use of the equipment, develop applications for the techniques available and train the researchers in preparing samples, using the equipment and the applications, and processing data. Moreover, the unit managers use their technical and scientific expertise to assist in the institute research projects. In 2009, the area had sixteen technicians.


2. RESEARCH Research Support Area

Nuclear Magnetic Resonance Unit Unit Manager: Dr. Gabriel González Unit Technician: Kerman Gómez THE UNIT

MOST IMPORTANT EQUIPMENT

The Nuclear Magnetic resonance (NMR) Unit was created in 2004 when it acquired its first spectrometer. It provides researchers with access to automatic or manual NMR experiments. It also advises researchers about which experiment will be most appropriate to their needs. It trains and teaches researchers about how to use NMR, what information can be obtained from NMR experiments and how to optimize the instrumental resources available.

„„ Two Bruker Avance 400 Ultrashield NMR spectrometers.

The techniques available up to now guarantee access to all kinds of NMR experiments in liquid phase for a wide range of nuclei and in gel phase for the more common nuclei (1H and 13 C). The NMR unit has successfully introduced researchers to such uncommon techniques as heteronuclear (mono and bidimensional) experiments, diffusion experiments and kinetic measurements.

„„ One Bruker Avance 500 Ultrashield NMR spectrometer. „„ BBI (Broadband Inverse), BBO (Broadband Observe) and 19 F Selective probes for the above mentioned instruments, all of them with ATM and z-gradients. The 500 instrument has also an HR-MAS probe for gel-phase samples and a TBO (Triple Broadband Observe) probe in combination with a third channel. „„ Two BACS autosamplers (60 and 120 positions) for the two 400 instruments.

The NMR unit provides researchers with a very wide range of tools, from all kinds of automatic NMR experiments to numerous special NMR experiments which are usually available upon demand. Another service provided by the NMR unit is that researchers can be supplied with NMR material (different types of NMR tubes and deuterated solvents), and advised about special NMR materials which may be of use for their special needs. The staff of the NMR Unit also organizes training activities, so that researchers can learn which experiments are most appropriate, how they can optimize the information obtained from NMR experiments, and how they can use the tools available (mainly computer ones). These activities range from training new users how to obtain NMR spectra automatically and how to use NMR processing software (TOPSPIN), to more general courses about the NMR experiments available and the information they can provide.

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2. RESEARCH Research Support Area

X-Ray Diffraction Unit Unit Manager: Dr. Jordi Benet-Buchholz Unit Technicians: Eduardo Escudero / Dr. Marta Martínez THE UNIT

MOST IMPORTANT EQUIPMENT

The X-ray Diffraction Unit gathers all the techniques which are based on the diffraction of X-rays on crystalline solids. This Unit started to work at the end of 2004 with the acquisition and installation of the main devices. In this Unit two principal techniques are available: Powder X-ray Diffraction and Single Crystal X-ray Diffraction.

„„ Single Crystal X-ray diffraction System: Bruker-Nonius diffractometer equipped with an APPEX 2 4K CCD area detector, a FR591 rotating anode with _MoKα1 radiation, Montel mirrors as monochromator and a Kryoflex low temperature device (T = 100 K). Programs available: Data collection Apex2 V. 1.0-22 (Bruker-Nonius 2004), data reduction Saint+ Version 6.22 (Bruker-Nonius 2001) and absorption correction SADABS V. 2.10 (2003). Crystal structure solution and refinement as implemented in SHELXTL Version 6.10 (Sheldrick, Göttingen University (Germany), 2000). Refinement also with the Multipol Refinement Program XD 4.1.

The Powder X-ray Diffraction technique is used basically as a primary screening method and delivers a fingerprint of each different crystalline form analyzed. The Single Crystal X-ray Diffraction technique delivers a three-dimensional structure at atomic scale of a selected crystalline compound. The principal objective of the X-ray Diffraction Unit is giving support to the research groups and the Polymorphism R&D Unit located at the ICIQ in the characterization of their chemical compounds which are available in a crystalline state. The powder X-ray diffraction method gives a basic service to all users at the ICIQ with a system which allows easy sample preparation and short measuring time for a high number of samples. In contrast, the single crystal X-ray diffraction method is highly specialized with a system fitted together from high performance components. The objective in this case is to give a direct support to the research groups solving problems in all levels of difficulty. This support includes the crystallization of problematic samples, the preparation of crystals of poor quality and the refinement of troubling datasets.

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„„ Powder X-ray diffraction System: D8 Advance Series 2Theta/Theta powder diffraction system using CuKα1-radiation in transmission geometry. The system is equipped with a VÅNTEC- 1 single photon counting PSD, a germanium monochromator, a ninety-position auto changer sample stage, fixed divergence slits and a radial soller. Programs available: Data collection with DIFFRAC plus XRD Commander V.2.4.1 and evaluation with EVA V.12.0 and TOPAS V.6. „„ Microscope: Zeiss Stemi SV11 Stereomicroscope (magnification: x 15-170).


2. RESEARCH Research Support Area

High Resolution Mass Spectrometry Unit Unit Manager: Dr. Noemí Cabello Unit Technician: Alba González THE UNIT

MOST IMPORTANT EQUIPMENT

The High Resolution Mass Spectrometry Unit provides ICIQ researchers with access to state-of the-art mass spectrometry instruments capable of characterising the wide range of compounds which are typically of interest in the institute. The apparatus include most ionization options, sample introduction and chromatographic techniques which are required for mass spectrometry problem solving in chemistry.

Three mass spectrometers have been acquired since the facility was set up in 2004:

All the instruments have excellent sensitivity (< pmol), mass resolution (FWHM > 10000) and accuracy (< 3 mDa for small molecules), facilitating target compound and impurity characterisation by elemental composition determination and isotopic pattern analysis. In addition to routine sample analysis, the unit also supports research projects which are more dependent on mass spectrometry experiments, such as mechanistic studies, intermediate identification, or biochemical applications.

„„ Waters GCT gas chromatography coupled to time-of-flight mass spectrometry (GC/MS-TOF) with electron ionisation (EI) and chemical ionisation (CI) options. „„ Waters LCT Premier liquid chromatography coupled to time-of-flight mass spectrometer (HPLC/MS-TOF) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) options. „„ BRUKER Autoflex matrix assisted laser desorption ionization (MALDI) time-of-flight mass spectrometer.

The unit provides comprehensive training for ICIQ researchers to ensure optimal use of the facility and appropriate data interpretation.

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2. RESEARCH Research Support Area

Chemical Reaction Technologies Unit Unit Manager: Dr. Gisela Colet Laboratory Manager: Dr. Marta Giménez Unit Technicians: Mariona Urtasun / Dr. Yvette Mata THE UNIT

MOST IMPORTANT EQUIPMENT

The Chemical Reaction Technologies Unit was created in 2009 when the former Parallel Synthesis & Process Chemistry Unit incorporated the miroflow reactors belonging to the ICIQ Marie Curie Unit led by Prof. van Leeuwen. This Unit provides ICIQ researchers with technical support in chemical reaction development, with special emphasis on reaction parallelization and high throughput synthesis, reaction scale up, in situ reaction monitoring, reactions under high pressure conditions and microflow reactions.

„„ A computer controlled, liquid phase parallel chemical synthesizer, provided with automatic liquid handling, 16 reactors of 20 mL and 4 reactors of 50 mL (MultiMax from Mettler Toledo).

In the ambit of chemical parallelization, the Unit has equipment to cover all the unit operations involved in a chemical process: reaction, work-up, purification and final isolation of the product. A chemical reaction can be scaled up, in a totally computer controlled reactor, from 0.6 to 6 L. This scale is optimal for preparing in-house starting materials and for technology transfer in cooperation projects.

In situ reaction monitoring can be performed either by heat flow calorimetry or by FTIR spectroscopy. These techniques are non intrusive and are very useful for kinetic and mechanistic studies. In order to promote reactions by different energy sources microwave and photochemical reactors are also accessible. Moreover the set of microflow reactors allows performing microflow reactions under different conditions.

„„ A computer controlled platform for liquid additions configured to adapt liquid and solid phase parallel reaction blocks: 6x50 mL, 12x25 mL and 24x10 mL (Minimapper from Mettler Toledo). „„ A computer controlled parallel pressure chemical synthesizer with 16 autoclaves of 15 mL and automatic liquid handling (SPR-16 from AMTEC). „„ Several high pressure individual reactors with working volumes from 10 to 750 mL and the possibility to work up to 180ºC and 100 bar. „„ A photochemical reactor (Rayonet RPR-200). „„ A microwave reactor with working volumes from 0.5 to 7mL provided with a sample exchange robot (CEM Explorer). „„ A platform for automatic sequential liquid-liquid extraction and phase separation (ALLEXis from Mettler Toledo). „„ A parallel centrifugal evaporator (Genevac EZ-2). „„ A preparative flash chromatography system (Combiflash Companion 4x from ISCO). „„ A computer controlled laboratory chemical reactor with working volumes of 0.6, 2.0 and 6.0 L (LabMax from Mettler Toledo). „„ A system to monitor chemical reactions in situ by FTIR adaptable to chemical reactors from 1mL to 6L (React IR 4000 from Mettler Toledo). „„ An autoclave to monitor reactions under high pressure conditions by FTIR. „„ A small volume reaction calorimeter ( Super CRC from Omnicaltech). „„ Four microflow reaction systems: two systems for homogeneous liquid-liquid reactions, one equipment for simple reactions and one for cascade or consecutive reactions. One for heterogeneous solid-liquid reactions. And one for high pressure gas-liquid reactions (up to 20 bar)

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2. RESEARCH Research Support Area

Chromatography, Thermal Analysis and Electrochemistry Unit Unit Manager: Enrique Cequier Unit Technician Simona Curreli THE UNIT

MOST IMPORTANT EQUIPMENT

The Chromatography, Thermal Analysis and Electrochemistry Unit was created in 2009 as a split of the former General Scientific Instrumentation Unit (2004-2008) and is focused to provide support to ICIQ researchers in the mentioned techniques.

„„ Two Agilent Technologies (1100 and 1200 series) high performance liquid chromatographs. Agilent 1100 is equipped with UV-Vis diode array, fluorescence, evaporative light scattering and single quadrupole mass spectrometer detectors. The Agilent 1200 is equipped with an UV-Vis diode array detection.

Regarding chromatography, the Unit is equipped with two high performance liquid chromatographs (HPLC) coupled to diode array and mass spectrometer detectors, among other type of detection, a semi preparative HPLC to scale up purifications and three gas chromatographs (GC) coupled to flame ionization and mass spectrometer detectors. Thermal analysis and calorimetric techniques are available through a differential scanning calorimeter, a thermobalance and an isothermal titration microcalorimeter, the latter used for accurate determinations of binding constants, reaction stoichiometry, and enthalpy and entropic values. Regarding electrochemistry instrumentation, the Unit has two potentiostats (one dedicated to photosensitive compounds in a dark laboratory) and two titrators: Karl Fischer and potetiometric. Moreover, unit technicians are responsible for the management of the open use instrumentation such as three glove boxes, and four solvent purification systems.

„„ Three Agilent Technologies 6890N/G1530N gas chromatographs, two with a mass selective detector and the other with a FID and TCD detectors. „„ A Waters 600 semi preparative high performance liquid chromatograph with dual wavelength detection. „„ A Microcal VP-ITC isothermal titration microcalorimeter. „„ A Mettler Toledo DSC 822e differential scanning calorimeter. „„ A Mettler Toledo SDTA 851e thermo balance. „„ A Princeton Applied Research PARSTAT 2273 potentiostat/ galvanostat. „„ A BioLogic SP-150 potentiostat with low current option and external power booster. „„ Three MBraun UNILAB glove boxes. „„ Three Innovative Technology SPS-400 solvent purification systems with six dry solvent dispensers each one. „„ A MBraun SPS-800 with five dry solvent dispensers.

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2. RESEARCH Research Support Area

Heterogeneous Catalysis Unit Unit Manager: Dr. Miguel Antonio González THE UNIT

MOST IMPORTANT EQUIPMENT

It was inaugurated in 2006 with the aim of providing support to the researchers of the institute working in heterogeneous catalysis (gas phase reactions catalyzed by solids). To that purpose, some state-of-the-art techniques for the catalysts characterization and testing are available in the unit. Namely, the apparatus and related techniques are the following:

„„ AUTOSORB 1 MP (QUANTACHROME). Physisorption analyzer for the textural characterization of solids. Isotherms of N2 at 77K, also of Ar at 87K on special request, provide information on the porous network of the solid. „„ micro-Ultrapycnometer 1200e (QUANTACHROME). By gas displacement, it measures the density of solids without considering the volume occupied by the pores (skeletal density). „„ TPDRO 1100 (Thermofisher). The TPD/R/O (Temperature Programmed Desorption/Reduction/Oxidation) and pulse chemisorption experiments allow studying the reactivity or affinity of the catalyst active sites with active molecules contained in a gas stream. „„ Microactivity Reference (PID Eng&Tech). It is a compact fixed bed reactor set-up for catalytic activity experiments. It can operate up to 1000 ºC, up to 100 bar and with up to seven different compounds (including one vapour) in the feed gas stream. „„ OMNISTAR (Pfeiffer) and 6890N (Agilent). MS and GC are used for the on-line analysis of gas streams. „„ TAP-2 reactor (Mithra Technologies). The TAP (Temporary Analysis of Products) is a cutting edge and not commonly found dynamic technique in which the reactants are pulsed into a catalytic microreactor under high vacuum. A MS probe is located just at the reactor outlet, leading to a time resolution in the sub-milisecond order. It is one of the most powerful tools in the elucidation of reaction mechanisms and pathways. It has shown a great utility not only in the fundamental understanding of catalytic processes, but also in the resolution of problems at an industrial level (e.g. side-reactions minimization in the NH3 oxidation of nitric acid production).

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2. RESEARCH Research Support Area

Photophysics Unit Unit Manager: Dr. Javier Pérez Hernández THE UNIT

MOST IMPORTANT EQUIPMENT

Created in 2006, the Photophysics Unit provides ICIQ researchers with equipment for observing induced physicochemical processes, such as luminescence, electron transfer or energy transfer, both in solution and in solid-state samples. Moreover, in a highly applied research level, this laboratory also has equipment dedicated to the characterization of molecular photovoltaic and organic LEDs devices.

„„ Transient absorption spectroscopy system. The optic bench is composed of an excitation source of nitrogen laser PTI 3300 with laser dye unit GL-301, which provides a variable wavelength source of excitation (400-700 nm); a 150 W tungsten lamp used as the probe-light source; 2 monochromators PTI M101; photodetector and oscilloscope Tektronix TDS200.

Regarding photophysical characterization, steady state of singlet and triplet emission, emission lifetime, and charge recombination lifetime processes are observable by the equipment available in the Unit. Furthermore, since an important part of the measurements are based on the characterization of electrical properties of molecular devices, the Unit has an electronic workbench in order to develop dedicated instrumentation software and hardware, which are not commercially available. In this sense, prototypes developed in house are employed for the characterization of dye and organic solar cells, such as voltage-current tracer, and quantum efficiency equipment. The purpose of these prototypes is to simplify and boost the accuracy of the measurement process. Moreover, a protocol for laser safety has been incorporated to the Unit and special training on laser measurements is given to ICIQ researchers.

„„ Fluorimeter Aminco-Bowman Series 2. Equipment composed by a xenon lamp and four temperature-regulated cuvette holders (20-60 ºC). Wavelength range: 250-850 nm. „„ LifeSpec-red (Edinburgh Instruments). Time correlated single photon counting system for lifetime emission from 30 picoseconds to 10 miliseconds, with wavelength response of 200-850 nm. Data acquisition board TCC900 32 bits, 33 MHz. Control and analysis software F900 and FAST. Several pulsed diode lasers at 405 nm, 505 nm and 635 nm. „„ Solar simulator and VI tracer. Abet 150 W xenon lamp and Keithley 2400. All the measurements are controlled by in house made software. „„ QE/IPCE measurement kit. Oriel 150 W xenon lamp, PTI M-101 motorized monochromator, 4” integrating sphere and Keithley 2400. In house made software controls all the measurement procedure. „„ OLEDs characterization system. Minolta LS 110 luminance meter and Keithley 2400. The measurement process is controlled by in house made software. „„ Metal and organic molecule evaporator. System composed by an Mbraun inert gas glove box, which includes a high vacuum chamber (1x10-6 mBar) with four electro-thermal sources for metal and molecule evaporation. This system allows the control of film thickness from 5 up to 300 nanometers.

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2. RESEARCH Research Support Area

Spectroscopy and Kinetics Unit Unit Manager: Dr. Fernando Bozoglián THE UNIT

MOST IMPORTANT EQUIPMENT

The Spectroscopy and Kinetics Unit was created in July 2009 as a split of the former General Instrumentation Unit. This Unit provides ICIQ researchers with technical support in different spectroscopic techniques as well as in kinetic reaction mechanism studies.

„„ Spectrophotometer Lambda 1050 from Perkin Elmer: Spectrophotometer with three-detector module: PMT, InGaAs and PbS for the entire UV/Vis/NIR range (175 to 3300 nm). Its high sensitivity allows to go down to 0.2 nm resolution in the NIR region.

The current instrumentation of the Unit allows acquisition of UV-Vis-NIR, FTIR, FT-Raman, Circular Dichroism and Fluorescence spectra as well as polarimetric measurements. A fast mixing stopped flow module with an ultra-fast UV-Vis detector is also available for kinetic analysis of fast chemical reactions in the millisecond time scale.

„„ Spectrophotometer UV-Vis UV-2401PC from Shimadzu: Double beam, single monochromator UV-Vis spectrophotometer with photomultiplier tube detector. Range 190-900 nm, resolution 0.1 nm.

The Unit also gives advice to researchers in the design of experiments in order to elucidate reaction mechanisms. Kinetics can also be monitored using instrumentation available in other Units of the institute. The tasks of the Unit from a mechanistic viewpoint are, among others, treatment, fitting and interpretation of kinetic data. Moreover, the Unit trains the users in order to achieve optimal use of the instruments.

„„ Spectrometer FT-IR 5700 with FTRaman Module from ThermoNicolet: FT-IR spectrometer with DTLGS and MCT detector, FT-Raman module and drift cell accessory. „„ Polarimeter P-1030 from Jasco: This instrument has a Photomultiplier tube detector, angular range: ± 90 º and measurement speed better than 6 º s-1. „„ Circular Dichroism spectrometer Chirascan from Applied Photophysics: This instrument measures simultaneous UV-Vis and CD spectra in the range 165 to 900 nm. The device is equipped with a peltier thermal control unit (-40/+100ºC) with possibility of temperature ramp control. „„ Fluorimeter Aminco Bowman Series 2 from Thermo Nicolet: System composed by a continuum and a pulsed Xenon lamps, four temperature-controlled cuvettes holder (20-60ºC) and a solid sample holder. Wavelength range: 250-850 nm. „„ Fast mixing stopped flow module SFM300 from Bio-Logic: This module has three syringes controlled independently, that allow simple or double mixing, different mixing ratios and submilisecond mixing time. The system is completed with a cryostat Huber CC3-905 VPCw (-90 ºC to +100 ºC) and a fast UV-Vis Diode Array spectrophotometer TIDAS capable of recording one spectrum in 0.8 ms.

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2. RESEARCH Current Projects

2.3 Current Projects EUROPEAN PROJECTS Title

Total amount

Period

Group Leader

736.380 €

2006 – 2009

Piet Van Leeuwen

43.200 €

2006 – 2009

Emilio Palomares

 European solar fuel initiative (SOLAR H2)

174.570 €

2008 – 2010

Antoni Llobet

 Actinide Recycling by separation and transmutation (ACSEPT)

210.000 €

2008 – 2010

Javier de Mendoza

 Efficient and robust Dye sensitized solar cells and modules (ROBUST)

302.520 €

2008 – 2010

Emilio Palomares

1.300.000 €

2009 – 2014

Emilio Palomares

 Studio classroom integrated homogeneous catalysis using

microelectronic flow systems: introducing a new era in catalysis research (VISION CATALYSIS)

 Coordination Action towards stable and low-cost organic solar cell Technologies and their application (ORGAPVNET)

 Control of the Electronic Properties in Hybrid-Quantum Dot/ Polymer-Materials for Energy Production (POLYDOT)

SPANISH AND CATALAN PROJECTS Title

 Diseño de Catalizadores para una Química Sostenible: Una Aproximación Integrada (INTECAT)

 Nuevos dispositivos fotovoltaicos moleculares: conceptos y tecnologías de fabricación (FOTOMOL)

 Catálisis redox y sus aplicaciones e implicaciones: un enfoque multidisciplinar

 Estudio de moléculas optica y electroquimicamente activas y sus aplicaciones en dispositivos fotovoltaicos moleculares

Total amount

Period

Group Leader

4.900.000 €

15/09/2006 14/09/2011

Miquel A. Pericàs

529.000 €

01/01/2008 31/06/2009

Emilio Palomares

106.480 €

01/10/2007 31/09/2010

Antoni Llobet

133.100 €

01/10/2007 31/09/2010

Emilio Palomares

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2. RESEARCH Current Projects

Title

 Nuevos métodos y catalizadores para la actividad electrófila de moleculas organicas

 Ligandos y catalizadores soportados: hacia el desarrollo de materiales inteligentes con comportamiento similar a enzimas

 Aproximaciones modulares, covalente y supramolecular, a la catálisis asimétrica

 Catálisis innovadora  De complejos monometálicos a Clusters polinucleares y superficies: Aplicaciones en catálisis y nanociencia

 Cavidades moleculares para catálisis, separación de fullerenos y procesos de transfferencia electrónica

 Ensamblajes moleculares funcionales.

Investigación básica y simples aplicaciones

 Interpretación molecular de los mecanismos dE la catálisis homogénea: acoplamiento cruzado y activación C-H

 Estudio de reacciones complejas en catálisis heterogénea por métodos a primeros principios

 Diseño racional de procesos catalíticos más eficientes a través de conocimiento mecanístico

Total amount

Period

Group Leader

417.450 €

01/10/2007 31/09/2010

Antonio M. Echavarren

643.478 €

01/01/2009 31/12/2013

Miquel A. Pericàs

121.000 €

01/01/2009 31/12/2011

Anton Vidal

133.100 €

01/01/2009 31/12/2011

Piet van Leeuwen

60.500 €

01/01/2009 31/12/2011

Carles Bo

249.986 €

01/01/2009 31/12/2011

Javier de Mendoza

185.735 €

01/01/2009 31/12/2011

Pau Ballester

104.665 €

01/01/2009 31/12/2011

Feliu Maseras

60.500 €

01/10/2006 30/09/2009

Núria López

96.800 €

01/10/2006 30/09/2009

Javier Pérez-Ramírez

143.990 €

01/01/2009 31/12/2011

Arjan Kleij

 Síntesis orgánica con plantillas obtenidas a partir de ligandos Salen: nuevas estrategias hacia la cooperatividad multimetálica en la catálisis homogénea

 AGAUR: Ajuts per a Grups de Recerca (SGR2009)

82

70.720 €

01/10/2009 30/09/2013

Antonio M. Echavarren

52.000 €

01/10/2009 30/09/2013

Miquel A. Pericàs

47.840 €

01/10/2009 30/09/2013

Pau Ballester

49.920 €

01/10/2009 30/09/2013

Feliu Maseras

65.520 €

01/10/2009 30/09/2013

Emili Palomares

42.640 €

01/10/2009 30/09/2013

Antoni Llobet

42.640€

01/10/2009 30/09/2013

Javier Pérez-Ramírez


3

Scientific Output T

he ICIQ is commited to ensuring that the consolidation of the current research lines at the Institution, in the fields

of catalysis and methodologies for sustainable production, nanoscience and supramolecular chemistry, and renewable energies (photovoltaic energy and hydrogen photoproduction) will lead to outstanding scientific results which will be gathered in high-level publications. If the ICIQ works as it was designed for, the research personnel will participate in some of the most important Chemical challenges of our Century and the results of their research will stimulate the strengthening of the technology base of the Catalan business sector.

83


3. SCIENTIFIC OUTPUT ICIQ Publications

3.1 ICIQ Publications 1. Asymmetric organocatalytic cascade reactions with α-substituted α,β-unsaturated aldehydes

9. Oxygen-oxygen bond formation pathways promoted by ruthenium complexes

P. Galzerano, F. Pesciaioli, A. Mazzanti, G. Bartoli, P. Melchiorre

S. Romain, L. Vigara, A. Llobet

Angew. Chem. Int. Ed. 2009, 48, 7892-7894

Acc. Chem. Res. 2009, 42, 1944-1953

2. Supramolecular-directed chiral induction in biaryl derivatives

10. Mercury optical fibre probe based on a modified cladding of sensitised Al2O3 nano-particles

J. Etxebarria, H. Degenbeck, A.-S. Felten, S. Serres, N. Nieto, A. Vidal-Ferran

J. Org. Chem. 2009, 74, 8794-8797

3. Continuous flow enantioselective arylation of aldehydes

J. Pérez-Hernández, J. Albero, E. Llobet, X. Correig, I. R. Matías, F. J. Arregui, E. Palomares

Sensors Actuat. B-Chem. 2009, 143, 103-110

with ArZnEt using triarylboroxins as the ultimate source of aryl groups

11. Stereospecific C-H oxidation with H2O2 catalyzed by a

J. Rolland, X. C. Cambeiro, C. Rodríguez-Escrich, Miquel A. Pericàs

L. Gómez, I. Garcia-Bosch, A. Company, J. Benet-Buchholz, A. Polo, X. Sala, X. Ribas, M. Costas

Beilstein J. Org. Chem. 2009, 5, 56

4. A highly selective, polymer-supported organocatalyst for Michael additions with enzyme-like behavior E. Alza, M. A. Pericàs

Adv. Synth. Catal. 2009, 351, 3051-3056

5. Solid-phase synthesis of chiral bicyclic guanidinium oligomers V. Martos, P. Castreño, M. Royo, F. Albericio, J. de Mendoza

J. Comb. Chem. 2009, 11, 410-421

6. Synthesis and structure of novel RuII–N≡C–Me complexes and their activity towards nitrile hydrolysis: An examination of ligand effects J. Mola, D. Pujol, M. Rodríguez, I. Romero, X. Sala, N. Katz, T. Parella, J. Benet-Buchholz, X. Fontrodona, A. Llobet

Aust. J. Chem. 2009, 62, 1675-1683

7. Cationic rhodium (I) complexes of N-phosphino-tert-butylsulfinamide ligands: Synthesis, structure, and coordination modes T. Achard, J. Benet-Buchholz, A. Riera, X. Verdaguer

Organometallics 2009, 28, 480-487

chemically robust site-isolated iron catalyst

Angew. Chem. Int. Ed. 2009, 48, 5720-5723

12. DNA-cleavage induced by new macrocyclic Schiff base dinuclear Cu(I) complexes containing pyridyl pendant arms A. Arbuse, M. Font, M. A. Martínez, X. Fontrodona, M. J. Prieto, V. Moreno, X. Sala, A. Llobet

Inorg. Chem. 2009, 48, 11098-11107

13. The nature of M-B versus M=B bonds in cationic terminal borylene complexes: Structure and energy analysis in the borylene complexes [(η5-C5H5)(CO)2M{B(η5-C5Me5)}]+, [(η5-C5H5) (CO)2M(BMes)]+, and [(η5-C5H5)(CO)2M(BNMe2)]+ K. K. Pandey, A. Lledós, F. Maseras

Organometallics 2009, 28, 6442-6449

14. Chemodivergent metathesis of dienynes catalyzed by ruthenium–indenyl complexes: An experimental and computational study H. Clavier, A. Correa, E. C. Escudero-Adán, J. Benet-Buchholz, L. Cavallo, S. P. Nolan

Chem. Eur. J. 2009, 15, 10244-10254

15. Zeolite catalysts with tunable hierarchy factor by poregrowth moderators J. Pérez-Ramírez, D. Verboekend, A. Bonilla, S. Abelló

84

8. Brønsted acid catalyzed Morita–Baylis–Hillman reaction: A

Adv. Funct. Mater. 2009, 19, 3972-3979

new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations

16. Stereoselective gold-catalyzed cycloaddition of functiona-

G. W. Amarante, M. Benassi, H. M. S. Milagre, A. A. C. Braga, F. Maseras, M. N. Eberlin, F. Coelho

E. Jiménez-Núñez, K. Molawi, A. M. Echavarren

Chem. Eur. J. 2009, 15, 12460-12469

Chem. Commun. 2009, 7327-7329

lized ketoenynes: Synthesis of (+)-orientalol F


3. SCIENTIFIC OUTPUT ICIQ Publications

17. Formation of unusual trinuclear assemblies: Scope and mechanism of Zn(salphen)-templated activation of pyridinealcohol substrates

27. Synthesis of the tetracyclic core skeleton of the lundurines

M. Martínez Belmonte, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

Tetrahedron 2009, 65, 9015-9020

Eur. J. Inorg. Chem. 2009, 5307-5318

by a gold-catalyzed cyclization C. Ferrer, A. Escribano-Cuesta, A. M. Echavarren

18. Water oxidation at a tetraruthenate core stabilized by

28. The mechanism of the catalytic functionalization of haloalkanes by carbene insertion: An experimental and theoretical study

polyoxometalate ligands: Experimental and computational evidence to trace the competent intermediates

J. Urbano, A. A. C. Braga, F. Maseras, E. Álvarez, M. M. Díaz-Requejo, P. J. Pérez

A. Sartorel, P. Miró, E. Salvadori, S. Romain, M. Carraro, G. Scorrano, M. Di Valentin, A. Llobet, C. Bo, M. Bonchio

Organometallics 2009, 28, 5968-5981

J. Am. Chem. Soc. 2009, 131, 16051-16053

29. The Ru-Hbpp water oxidation catalyst

19. Modular synthesis of heterobimetallic salen structures

F. Bozoglian, S. Romain, M. Z. Ertem, T. K. Todorova, C. Sens, J. Mola, M. Rodríguez, I. Romero, J. Benet-Buchholz, X. Fontrodona, C. J. Cramer, L. Gagliardi, A. Llobet

using metal templation A. M. Castilla, S. Curreli, E. C. Escudero-Adán, M. Martínez Belmonte, J. Benet-Buchholz, A. W. Kleij

J. Am. Chem. Soc. 2009, 131, 15176-15197

Org. Lett. 2009, 11, 5218-5221

30. Anchoring of rare-earth-based single-molecule magnets

20. Epoxidation catalysts derived from aluminium and gallium dawsonites

S. Kyatskaya, J. R. Galán Mascarós, L. Bogani, F. Hennrich, M. Kappes, W. Wernsdorfer, M. Ruben

G. Stoica, M. Santiago, P. A. Jacobs, J. Pérez-Ramírez, P. P. Pescarmona

J. Am. Chem. Soc. 2009, 131, 15143-15151

Appl. Catal. A-Gen. 2009, 371, 43-53

on single-walled carbon nanotubes

31. A highly active catalyst for Huisgen 1,3-dipolar cycloaddi-

21. A DFT/MM analysis of the effect of ligand substituents on

tions based on the tris(triazolyl)methanol-Cu(I) structure

asymmetric hydrogenation catalyzed by rhodium complexes with phosphine-phosphinite ligands

S. Özçubukçu, E. Ozkal, C. Jimeno, M. A. Pericàs

S. M. A. Donald, A. Vidal-Ferran, F. Maseras

Org. Lett. 2009, 11, 4680-4683

22. Palladium-catalyzed direct carboxylation of aryl bromides

32. Increasing the performance of cis-dithiocyanato(4,40-dicarboxy-2,20-bipyridine)(1,10-phenanthroline) ruthenium (II) based DSC using citric acid as co-adsorbant

with carbon dioxide

A. Reynal, E. Palomares

A. Correa, R. Martín

Energy Environ. Sci. 2009, 2, 1078-1081

Can. J. Chem. 2009, 87, 1273-1279

J. Am. Chem. Soc. 2009, 131, 15974-15975

23. Towards a computational treatment of polyoxometalates in solution using QM methods and explicit solvent molecules P. Miró, J. M. Poblet, J. B. Ávalos, C. Bo

Can. J. Chem. 2009, 87, 1296-1301

24. Mn(II) complexes containing the polypyridylic chiral ligand (-)-pinene[5,6]bipyridine. Catalysts for oxidation reactions J. Rich, M. Rodríguez, I. Romero, L. Vaquer, X. Sala, A. Llobet, M. Corbella, M.-N. Collomb, X. Fontrodona

Dalton Trans. 2009, 8117-8126

33. A solid-supported organocatalyst for highly stereoselective, batch, and continuous-flow Mannich reactions E. A l z a , C. R o d r í g u e z -E s c r i c h , S. S a y a l e r o , A. B a s t e r o , M. A. P e r i c à s

Chem. Eur. J. 2009, 15, 10167-10172

34. Towards continuous flow, highly enantioselective allylic amination: Ligand design, optimization and supporting D. Popa, R. Marcos, S. Sayalero, A. Vidal-Ferran, M. A. Pericàs

Adv. Synth. Catal. 2009, 351, 1539-1556

35. Evolution of propargyl ethers into allylgold cations in the

25. Vinyl acetate synthesis on homogeneous and heterogeneous

cyclization of enynes

Pd-based catalysts: A theoretical analysis on the reaction mechanisms

E. Jiménez-Núñez, M. Raducan, T. Lauterbach, K. Molawi, C. R. Solorio, A. M. Echavarren

J. J. Plata, M. García-Mota, A. A. C. Braga, N. López, F. Maseras

J. Phys. Chem. A 2009, 113, 11758-11762

26. Photo-induced electron recombination dynamics in CdSe/ P3HT hybrid heterojunctions J. Albero, E. Martínez-Ferrero, J. Ajuria, C. Waldauf, R. Pacios, E. Palomares

Phys. Chem. Chem. Phys. 2009, 11, 9644-9647

Angew. Chem. Int. Ed. 2009, 48, 6152-6155

36. Synthesis of highly modular bis(oxazoline) ligands by Suzuki cross-coupling and evaluation as catalytic ligands X. Cattoën, M. A. Pericàs

Tetrahedron 2009, 65, 8199-8205

85


3. SCIENTIFIC OUTPUT ICIQ Publications

37. Supramolecular interactions in dye-sensitised solar cells

48. Amino thiols versus amino alcohols in the asymmetric

M. Planells, F. J. Céspedes-Guirao, L. Gonçalves, A. Sastre-Santos, F. Fernández-Lázaro, E. Palomares

alkynylzinc addition to aldehydes

J. Mater. Chem. 2009, 19, 5818-5825

S. Subirats, C. Jimeno, M. A. Pericàs

Tetrahedron Asymmetr. 2009, 20, 1413-1418

38. Complexation of potassium and ammonium ions with crown-ether-like rings

49. Charge recombination studies in conformally coated trifluoroacetate/TiO2 modified dye sensitized solar cells (DSSC)

A. Müller, F. L. Sousa, A. Merca, H. Bögge, P. Miró, J. A. Fernández, J. M. Poblet, C. Bo

A. Sánchez-Díaz, E. Martínez-Ferrero, E. Palomares

Angew. Chem. Int. Ed. 2009, 48, 5934-5937

39. Carbene or cation? A. M. Echavarren

Nature Chem. 2009, 1, 431-433

40. Determination of choline and derivatives with a solid-con-

J. Mater. Chem. 2009, 19, 5381-5387

50. Iron vs. ruthenium - A comparison of the stereoselectivity in catalytic olefin epoxidation J. Benet-Buchholz, P. Comba, A. Llobet, S. Roeser, P. Vadivelu, H. Wadepohl, S. Wiesner

Dalton Trans. 2009, 5910-5923

tact ion-selective electrode based on octaamide cavitand and carbon nanotubes

51. Metal-mediated multiporphyrin functional assemblies

J. Ampurdanés, G. A. Crespo, A. Maroto, M. A. Sarmentero, P. Ballester, F. X. Rius

J. Porphyr. Phthalocya. 2009, 13, 481-493

Biosens. Bioelectron. 2009, 25, 344-349

41. Kinetico-mechanistic insight into the platinum-mediated C-C coupling of fluorinated arenes

L. P. Hernández, A. González-Álvarez, A. I. Oliva, P. Ballester

52. The XXI challenge: Cheap and renewable energy sources E. Palomares

ChemSusChem 2009, 2, 267-268

T. Calvet, M. Crespo, M. Font-Bardia, K. Gómez, G. González, M. Martínez

Organometallics 2009, 28, 5096-5106

42. Assembly of unusual Zn-cluster compounds based on pyridinealcohol platforms

S. Fantasia, J. D. Egbert, V. Jurčík, C. S. J. Cazin, H. Jacobsen, L. Cavallo, D. M. Heinekey, S. P. Nolan

D. Anselmo, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

Angew. Chem. Int. Ed. 2009, 48, 5182-5186

Dalton Trans. 2009, 7368-7373

43. Thermodynamic characterization of the self-assembly process

54. Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a CuII complex

of a three component heterobimetallic bisporphyrin macrocycle

G. J. Christian, A. Arbuse, X. Fontrodona, M. A. Martinez, A. Llobet, F. Maseras

A. González-Álvarez, A. Frontera, P. Ballester

Dalton Trans. 2009, 6013-6020

J. Phys. Chem. B 2009, 113, 11479-11489

44. Metal-catalyzed carboxylation of organometallic reagents with carbon dioxide A. Correa, R. Martín

55. Efficient hydrogenation of alkenes using a highly active and reusable immobilised Ru complex on AlPO4 V. Caballero, F. M. Bautista, J. M. Campelo, D. Luna, R. Luque, J. M. Marinas, A. A. Romero, I. Romero, M. Rodríguez, I. Serrano, J. M. Hidalgo, A. Llobet

Angew. Chem. Int. Ed. 2009, 48, 6201-6204

J. Mol. Catal. A-Chem. 2009, 308, 41-45

45. Ligation of substituted pyridines to metallosalphen complexes –

56. Ru(II)-phthalocyanine sensitized solar cells: The influence

Crystallographic characterization of an unexpected four-component

of co-adsorbents upon interfacial electron transfer kinetics

supramolecular assembly comprising a sterically demanding ligand

A. Morandeira, I. López-Duarte, B. O’Regan, M. V. Martínez-Díaz, A. Forneli, E. Palomares, T. Torres, J. R. Durrant

E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

Eur. J. Inorg. Chem. 2009, 3562-3568

J. Mater. Chem. 2009, 19, 5016-5026

46. Na-dawsonite derived aluminates for DMC production by transesterification of ethylene carbonate

57. Functionalized nanoparticles as catalysts for enantioselective processes

G. Stoica, S. Abelló, J. Pérez-Ramírez

S. Roy, M. A. Pericàs

Appl. Catal. A-Gen. 2009, 365, 252-260

Org. Biomol. Chem. 2009, 7, 2669-2677

47. Extended π-aromatic systems for energy conversion:

58. Gold(I)-catalyzed intermolecular hydroalkoxylation of

Phthalocyanines and porphyrins in molecular solar cells

allenes: A DFT study

Y. Rio, P. Vazquez, E. Palomares

R. S. Paton, F. Maseras

J. Porphyr. Phthalocya. 2009, 13, 645-651

86

53. Activation of hydrogen by palladium(0): Formation of the mononuclear dihydride complex trans-[Pd(H)2(IPr)(PCy3)]

Org. Lett. 2009, 11, 2237-2240


3. SCIENTIFIC OUTPUT ICIQ Publications

59. Rhodium-catalyzed intermolecular hydroiminoacylation of alkenes: Comparison of neutral and cationic catalytic systems

70. Templated synthesis and site-selective conversion of

P. Marcé, C. Godard, M. Feliz, X. Yáñez, C. Bo, S. Castillón

A. M. Castilla, S. Curreli, N. M. Carretero, E. C. Escudero-Adán, J. BenetBuchholz, A. W. Kleij

Organometallics 2009, 28, 2976-2985

completely nonsymmetrical bis-metallosalphen complexes

Eur. J. Inorg. Chem. 2009, 2467-2471

60. Why is the Suzuki-Miyaura cross-coupling of sp carbons 3

in α-bromo sulfoxide systems fast and stereoselective? A DFT study on the mechanism C. Gourlaouen, G. Ujaque, A. Lledós, M. Medio-Simon, G. Asensio, F. Maseras

J. Org. Chem. 2009, 74, 4049-4054

61. Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching S. Abelló, A. Bonilla, J. Pérez-Ramírez

71. Gold-catalyzed reactions of 1,5- and 1,6-enynes with carbonyl compounds: Cycloaddition vs. metathesis A. Escribano-Cuesta, V. López-Carrillo, D. Janssen, A. M. Echavarren

Chem. Eur. J. 2009, 15, 5646-5650

72. Evaluation of catalysts for N2O abatement in fluidized-bed combustion M. Santiago, M. A. G. Hevia, J. Pérez-Ramírez

Appl. Catal. B-Environ. 2009, 90, 83-88

Appl. Catal. A-Gen. 2009, 364, 191-198

73. Anion-templated formation of supramolecular multinuclear assemblies

62. Self-assembly of dimeric tetraurea calix[4]pyrrole capsules

S. J. Wezenberg, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

P. Ballester, G. Gil-Ramírez

P. Natl. Acad. Sci. U.S.A. 2009, 106, 10455-10459

63. Calix[4]arene-based conical-shaped ligands for voltagedependent potassium channels V. Martos, S. C. Bell, E. Santos, E. Y. Isacoff, D. Trauner, J. de Mendoza

P. Natl. Acad. Sci. U.S.A. 2009, 106, 10482-10486

64. Desilication of ferrierite zeolite for porosity generation and improved effectiveness in polyethylene pyrolysis A. Bonilla, D. Baudouin, J. Pérez-Ramírez

J. Catal. 2009, 265, 170-180

65. Electron transfer dynamics in dye-sensitized solar cells utilizing oligothienylvinylene derivates as organic sensitizers

Chem. Eur. J. 2009, 15, 5695-5700

74. Flexible pores of a metal oxide-based capsule permit entry of comparatively larger organic guests A. Ziv, A. Grego, S. Kopilevich, L. Zeiri, P. Miro, C. Bo, A. Müller, I. A. Weinstock

J. Am. Chem. Soc. 2009, 131, 6380-6382

75. [Pd(NHC)(allyl)Cl] complexes: Synthesis and determination of the NHC percent buried volume (%Vbur) steric parameter H. Clavier, A. Correa, L. Cavallo, E. C. Escudero-Adán, J. Benet-Buchholz, A. M. Z. Slawin, S. P. Nolan

Eur. J. Inorg. Chem. 2009, 1767-1773

76. The role of amide ligands in the stabilization of Pd(II) tricoordinated complexes: Is the Pd–NR2 bond order single or higher? S. Moncho, G. Ujaque, P. Espinet, F. Maseras, A. Lledós

J. N. Clifford, A. Forneli, L. López-Arroyo, R. Caballero, P. de la Cruz, F. Langa, E. Palomares

Theor. Chem. Acc. 2009, 123, 75-84

ChemSusChem 2009, 2, 344-349

77. Click azide-alkyne cycloaddition for the synthesis of D-(–)-

66. Zinc-centred salen complexes: Versatile and accessible supramolecular building motifs

1,4-disubstituted triazolo-carbanucleosides J. Broggi, H. Kumamoto, S. Berteina-Raboin, S. P. Nolan, L. A. Agrofoglio

Eur. J. Org. Chem. 2009, 1880-1888

A. W. Kleij

Dalton Trans. 2009, 4635-4639

67. Theoretical investigation of the inversion parameter in Co3-sAlsO4 (s=0–3) spinel structures F. Tielens, M. Calatayud, R. Franco, J. M. Recio, J. Pérez-Ramírez, C. Minot

Solid State Ionics 2009, 180, 1011-1016

68. A Ru-Hbpp-based water-oxidation catalyst anchored on rutile TiO2 L. Francàs, X. Sala, J. Benet-Buchholz, Ll. Escriche, A. Llobet

78. Quantification of enhanced acid site accessibility in hierarchical zeolites – The accessibility index F. Thibault-Starzyk, I. Stan, S. Abelló, A. Bonilla, K. Thomas, C. Fernandez, J.-P. Gilson, J. Pérez-Ramírez

J. Catal. 2009, 264, 11-14

79. Indenylidene ruthenium complex bearing a sterically demanding NHC ligand: An efficient catalyst for olefin metathesis at room temperature H. Clavier, C. A. Urbina-Blanco, S. P. Nolan

ChemSusChem 2009, 2, 321-329

Organometallics 2009, 28, 2848-2854

69. DFT study on the complex reaction networks in the con-

80. Structure-function relationships in unsymmetrical zinc

version of ethylene to ethylidyne on flat and stepped Pd J. Andersin, N. Lopez, K. Honkala

J. Phys. Chem. C 2009, 113, 8278-8286

phthalocyanines for dye-sensitized solar cells J.-J. Cid, M. García-Iglesias, J.-H. Yum, A. Forneli, J. Albero, E. MartínezFerrero, P. Vázquez, M. Grätzel, M. K. Nazeeruddin, E. Palomares, T. Torres

Chem. Eur. J. 2009, 15, 5130-5137

87


3. SCIENTIFIC OUTPUT ICIQ Publications

81. Hybrid scorpionate/cyclopentadienyl titanium and zirco-

92. Synthesis of dimethyl carbonate by transesterification of

nium complexes with alkoxide and imido ligands

ethylene carbonate over activated dawsonites

A. Otero, J. Fernández-Baeza, A. Antiñolo, J. Tejeda, A. Lara-Sánchez, L. F. Sánchez-Barba, M. Sánchez-Molina, C. Bo, M. Urbano-Cuadrado

G. Stoica, S. Abelló, J. Pérez-Ramírez

Inorg. Chim. Acta 2009, 362, 2909-2914

82. Self-assembly of double-decker cages induced by coordination of perylene bisimide with a trimeric Zn porphyrin: Study of the electron transfer dynamics between the two photoactive components A. I. Oliva, B. Ventura, F. Würthner, A. Camara-Campos, C. A. Hunter, P. Ballester, L. Flamigni

Dalton Trans. 2009, 4023-4037

83. Highly active [Pd(μ-Cl)(Cl)(NHC)]2 (NHC = N-heterocyclic carbene)

in the cross-coupling of Grignard reagents with aryl chlorides C. E. Hartmann, S. P. Nolan, C. S. J. Cazin

Organometallics 2009, 28, 2915-2919

84. Agostic interactions in alkyl derivatives of sterically hindered tris(pyrazolyl)borate complexes of niobium M. Etienne, J. E. McGrady, F. Maseras

ChemSusChem 2009, 2, 301-304

93. Accelerated generation of intracrystalline mesoporosity in zeolites by microwave-mediated desilication S. Abelló, J. Pérez-Ramírez

Phys. Chem. Chem. Phys. 2009, 11, 2959-2963

94. Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions M.-N. Birkholz (née Gensow), Z. Freixa, P. W. N. M. van Leeuwen

Chem. Soc. Rev. 2009, 38, 1099-1118

95. Mesoporous metallosilicate zeolites by desilication: On the generic pore-inducing role of framework trivalent heteroatoms J. C. Groen, R. Caicedo-Realpe, S. Abelló, J. Pérez-Ramírez

Mater. Lett. 2009, 63, 1037-1040

Coord. Chem. Rev. 2009, 253, 635-646

96. Multivariate calibration analysis of colorimetric mercury

85. C-C Reductive elimination in palladium complexes, and the

J. Pérez-Hernández, J. Albero, X. Correig, E. Llobet, E. Palomares

sensing using a molecular probe

role of coupling additives. A DFT study supported by experiment

Anal. Chim. Acta 2009, 633, 173-180

M. Pérez-Rodríguez, A. A. C. Braga, M. Garcia-Melchor, M. H. Pérez-Temprano, J. A. Casares, G. Ujaque, A. R. de Lera, R. Álvarez, F. Maseras, P. Espinet

97. Carbenes: Synthesis, properties, and organometallic chemistry

J. Am. Chem. Soc. 2009, 131, 3650-3657

P. de Frémont, N. Marion, S. P. Nolan

86. Molecular catalysts that oxidize water to dioxygen X. Sala, I. Romero, M. Rodríguez, Ll. Escriche, A. Llobet

Angew. Chem. Int. Ed. 2009, 48, 2842-2852

Coord. Chem. Rev. 2009, 253, 862-892

98. Structural analysis of zincocenes with substituted cyclopentadienyl rings

QTAIM properties

R. Fernández, A. Grirrane, I. Resa, A. Rodríguez, E. Carmona, E. Alvarez, E. Gutiérrez-Puebla, A. Monge, J. M. López del Amo, H.-H. Limbach, A. Lledos, F. Maseras, D. del Rio

J. I. Rodríguez, R. F. W. Bader, P. W. Ayers, C. Michel, A. W. Götz, C. Bo

Chem. Eur. J. 2009, 15, 924-935

87. A high performance grid-based algorithm for computing

Chem. Phys. Lett. 2009, 472, 149-152

88. Di-platinum complexes containing thiolato-urea ligands:

99. Oxygen-oxygen bond formation by the Ru-Hbpp water oxidation catalyst occurs solely via an intramolecular reaction pathway

Structural and anion binding studies

S. Romain, F. Bozoglian, X. Sala, A. Llobet

C. Mendoza, J. Benet-Buchholz, M. A. Pericàs, R. Vilar

J. Am. Chem. Soc. 2009, 131, 2768-2769

Dalton Trans. 2009, 2974-2985

89. Protonation of transition-metal hydrides: A not so simple process M. Besora, A. Lledós, F. Maseras

Chem. Soc. Rev. 2009, 38, 957-966

90. Cyclic oligomers based on complementary Zn(II) and

100. Synthesis of (±)-1,2,3-triazolo-30-deoxy-40-hydroxymethyl carbanucleosides via ‘click’ cycloaddition J. Broggi, N. Joubert, S. Díez-González, S. Berteina-Raboin, T. Zevaco, S. P. Nolan, L. A. Agrofoglio

Tetrahedron 2009, 65, 1162-1170

Sn(IV)-porphyrins

101. Gold-catalyzed olefin cyclopropanation

G. A. Metselaar, P. Ballester, J. de Mendoza

A. Prieto, M. R. Fructos, M. M. Díaz-Requejo, P. J. Pérez, P. Pérez-Galán, N. Delpont, A. M. Echavarren

New J. Chem. 2009, 33, 777-783

91. Trapping of a four-coordinate zinc salphen complex inside

Tetrahedron 2009, 65, 1790-1793

a crystal matrix

102. C-C coupling constants, JCC, are reliable probes for α-C-C

E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

agostic structures

Chem. Eur. J. 2009, 15, 4233-4237

C. Boulho, T. Keys, Y. Coppel, L. Vendier, M. Etienne, A. Locati, F. Bessac, F. Maseras, D. A. Pantazis, J. E. McGrady

Organometallics 2009, 28, 940-943

88


3. SCIENTIFIC OUTPUT ICIQ Publications

103. [(NHC)AuCl]-catalyzed Meyer–Schuster rearrangement:

113. Toxicity of copper(I)–NHC complexes against human tumor

Scope and limitations

cells: Induction of cell cycle arrest, apoptosis, and DNA cleavage

R. S. Ramón, N. Marion, S. P. Nolan

Tetrahedron 2009, 65, 1767-1773

M.-L. Teyssot, A.-S. Jarrousse, A. Chevry, A. de Haze, C. Beaudoin, M. Manin, S. P. Nolan, S. Díez-González, L. Morel, A. Gautier

104. Molecular recognition of pyridine N-oxides in water using calix[4]pyrrole receptors

114. Mechanism of the [(NHC)AuI]-catalyzed rearrangement

B. Verdejo, G. Gil-Ramirez, P. Ballester

Chem. Eur. J. 2009, 15, 314-318

of allylic acetates. A DFT study

J. Am. Chem. Soc. 2009, 131, 3178-3179

C. Gourlaouen, N. Marion, S. P. Nolan, F. Maseras

105. Access to hybrid supramolecular salen–porphyrin assemblies via a selective in situ transmetalation-metalation self-assembly sequence

115. Nonsymmetrical salen ligands and their complexes: Syn-

S. J. Wezenberg, G. A. Metselaar, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

Inorg. Chim. Acta 2009, 362, 1053-1057

106. Cationic NHC–gold(I) complexes: Synthesis, isolation, and

Org. Lett. 2009, 11, 81-84

thesis and applications A. W. Kleij

Eur. J. Inorg. Chem. 2009, 193-205

116. [(NHC)AuI]-catalyzed acid-free alkyne hydration at partper-million catalyst loadings

catalytic activity

N. Marion, R. S. Ramón, S. P. Nolan

P. de Frémont, N. Marion, S. P. Nolan

J. Am. Chem. Soc. 2009, 131, 448-449

J. Organomet. Chem. 2009, 694, 551-560

107. Gated and differently functionalized (new) porous capsules direct encapsulates' structures: Higher and lower density water T. Mitra, P. Miró, A.-R. Tomsa, A. Merca, H. Bögge, J. Bonet Ávalos, J. M. Poblet, C. Bo, A. Müller

Chem. Eur. J. 2009, 15, 1844-1852

108. Diastereoselectivity and molecular recognition of mercury(II) ions A. Reynal, J. Albero, A. Vidal-Ferran, E. Palomares

Inorg. Chem. Commun. 2009, 12, 131-134

109. Gold activation of nitriles: Catalytic hydration to amides R. S. Ramón, N. Marion, S. P. Nolan

Chem. Eur. J. 2009, 15, 8695-8697

110. Hydrogenation of C-C multiple bonds mediated by [Pd(NHC)(PCy3)] (NHC=N-heterocyclic carbene) under mild reaction conditions V. Jurčík, S. P. Nolan, C. S. J. Cazin

Chem. Eur. J. 2009, 15, 2509-2511

111. Mechanism of ammonia oxidation over PGM (Pt, Pd, Rh) wires

117. Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication J. Pérez-Ramírez, S. Abelló, A. Bonilla, J. C. Groen

Adv. Funct. Mater. 2009, 19, 164-172

118. Platinum(II) mediated Csp3-H activation of tetramethylthiourea S. Fantasia, A. Pasini, S. P. Nolan

Dalton Trans. 2009, 8107-8110

119. Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters: An experimental and theoretical study N.Marion, G.Lemière, A.Correa, C.Costabile, R.S.Ramón, X.Moreau, P.de Frémont, R.Dahmane, A.Hours, D.Lesage, J.-C.Tabet, J.-P.Goddard, V.Gandon, L.Cavallo, L.Fensterbank, M.Malacria, S.P.Nolan

Chem. Eur. J. 2009, 15, 3243-3260

120. Towards long-living metathesis catalysts by tuning the N-heterocyclic carbene (NHC) ligand on trifluoroacetamideactivated boomerang Ru complexes H. Clavier, F. Caijo, E. Borré, D. Rix, F. Boeda, S. P. Nolan, M. Mauduit

Eur. J. Org. Chem. 2009, 4254-4265

by temporal analysis of products and density functional theory

121. N-Heterocyclic carbenes in late transition metal catalysis

J. Pérez-Ramírez, E. V. Kondratenko, G. Novell-Leruth, J. M. Ricart

S. Díez-González, N. Marion, S. P. Nolan

J. Catal. 2009, 261, 217-223

Chem. Rev. 2009, 109, 3612-3676

112. Isolation and structural characterization of a binuclear in-

122. Highly efficient catalytic hydrodehalogenation of polychlorinated biphenyls (PCBs)

termediate species pertinent to transmetalation of Zn(salphen) complexes and the formation of polynuclear salen structures L. San Felices, E. C. Escudero-Adán, J. Benet-Buchholz, A. W. Kleij

S. Akzinnay, F. Bisaro, C. S. J. Cazin

Chem. Commun. 2009, 5752-5753

Inorg. Chem. 2009, 48, 846-853

89


3. SCIENTIFIC OUTPUT ICIQ Publications

123. A new quantitative structure–property relationship approach using dissimilarity measurements based on topological distances of non-isomorphic subgraphs

125. Effect of metal coordination on the interaction of substituted phenanthroline and pyridine ligands with quadruplex DNA J. E. Reed, A. J. P. White, S. Neidle, R. Vilar

Dalton Trans. 2009, 2558-2568

M. Urbano-Cuadrado, I. Luque Ruiz, M. Á. Gómez-Nieto

J. Math. Chem. 2009, 46, 853-865

124. Diastereoselective room-temperature Pd-catalyzed a-

126. Trends in ns2 np0 [M(CO)]q+ complexes: From germanium to element 114 (Uuq)

arylation and vinylation of arylmandelic acid derivatives

C. Gourlaouen, O. Parisel, J.-P. Piquemal

L. Jiang, S. Weist, S. Jansat

Chem. Phys. Lett. 2009, 469, 38-42

Org. Lett. 2009, 11, 1543-1546

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„„ The total number of published papers in journals with impact factor higher than 4,000 is 62 (49% of total number of published papers). „„ The total number of published papers in journals with impact factor higher than 3,000 is 91 (72% of total number of published papers). „„ Finally, the total number of published papers in journals with impact factor higher than 2,500 is 105 (83% of total number of published papers).


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3. SCIENTIFIC OUTPUT ICIQ Journal Covers

3.2 ICIQ Journal Covers Zeolite Catalysts with Tunable Hierarchy Factor by Pore-Growth Moderators

Formation of unusual trinuclear assemblies: Scope and mechanism of Zn(salphen)-templated activation of pyridinealcohol substrates

Adv. Funct. Mater. 2009, 19, 3972-3979

Eur. J. Inorg. Chem. 2009, 5307-5318

Self-assembly of dimeric tetraurea calix[4]pyrrole capsules

Zinc-centred salen complexes: Versatile and accessible supramolecular building motifs

P. Natl. Acad. Sc i. USA 2009, 106, 10455-10459

Dalton Trans. 2009, 4635-4639

Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication

Gated and differently functionalized (new) porous capsules direct encapsulates' structures: Higher and lower density water

Adv. Funct. Mater. 2009, 19, 164-172

92

Chem. Eur. J. 2009, 15, 1844-1852

Flexible pores of a metal oxide-based capsule permit entry of comparatively larger organic guests

Bite angle effects of diphosphines in Câ&#x20AC;&#x201C;C and Câ&#x20AC;&#x201C;X bond forming cross coupling reactions

J. Am. Chem. Soc. 2009, 131, 6380-6382

Chem. Soc. Rev. 2009, 38, 1099-1118


4

Technology Transfer A

fundamental aspect of ICIQâ&#x20AC;&#x2122;s mission is to improve the competitiveness of the chemical and pharmaceuti-

cal industries by pursuing an active policy to transfer the knowledge and technology developed at ICIQ and by promoting the creation of high-tech businesses.

According to this strategy, this year 2009 ICIQ has created Crysforma, a technology unit out of the former ICIQâ&#x20AC;&#x2122;s R&D Unit in Polymorphism, in order to strengthen its position in the sector and in the industry. This technology unit covers a basic need of the pharmaceutical industry, and is oriented to offer complete scientific and technological support in the field of pharmaceutical solid state development. Crysforma provides services for the discovery, analysis and scale-up of polymorphs, salts and co-crystals of active pharmaceuticals ingredients or intermediates. Besides, Crysforma has developed its own crystallization screening methodology based on the combination of several crystallization procedures. It is also expected that by late 2010 a technological unit on the development of catalysts is set up. Moreover, apart from signing several research projects contracts with the chemical and pharmaceutical industry, ICIQ has also seek the establishment of large collaborative research projects with companies. As a result of this strategy, the Esteve-ICIQ Joint Unit has been set up and by early 2010 the Henkel-ICIQ Joint Unit started its activities. Finally, ICIQ has also implemented an active policy of identifying and protecting industrial relevant inventions generated at ICIQ as industrial property.

93


4. PROJECTS Crysforma

4.1 Crysforma

Crysforma is a technology development unit of ICIQ, oriented to offer complete scientific support to pharmaceutical and fine chemicals companies in the field of pharmaceutical solid state development. Crysforma provides services for the discovery, analysis and scale-up of polymorphs, salts and co-crystals of active pharmaceutical ingredients (APIs) and intermediates.

Unit Manager: Dr. Jordi Cerón Business Development Manager: Irene Puntí Scientific Advisors: Dr. Lluís Solà / Dr. Jordi Benet-Buchholz Analytical Support: Dr. Fernando Bozoglián / Eduardo Escudero / Enrique Cequier Project Researchers: Dr. Jesús Ramírez / Dr. Laura Puig / Laia Pellejà / Dr. Gloria Freixas

94

Selecting the appropriate solid form of an API, first the optimal salt or co-crystal and then the most suitable polymorph or crystalline phase, is of key importance to the pharmaceutical and chemical industry. Choosing the optimal phase of an API assures optimum physical and chemical solid state properties: solubility, dissolution rate, hygroscopicity and stability. These properties can have a significant influence on the bioavailability of the final drug. Moreover, an adequate strategy on solid state development can strengthen and extend the patent protection of an API.


4. PROJECTS Crysforma

Crysforma has developed its own crystallization screening methodology, based on the combination of several crystallization procedures. We use high-throughput equipment controlled by highly skilled researchers in order to maximize the information gathered from each crystallization experiment. This methodology has also been successfully applied to the resolution of chiral compounds via diastereomeric salt formation. During 2009, Crysforma developed new water solubility and hygroscopicity determination methods, which complement its analytical preexisting capabilities, and provide additional value to Crysforma’s screening projects. Crysforma also worked intensively in the development of analytical methods for the quantification of polymorphic mixtures and crystalline / amorphous mixtures.

During 2009, Crysforma’s capabilities were promoted in several international events, such as the Polymorphism and Crystallization conference in Brussels, and the fairs Achema, in Frankfurt, and CPhI – ICSE which took place in Madrid. Type of projects: „„ Comprehensive polymorphism, salt and co-crystal screenings of a drug substance. „„ Scale-up of the optimal polymorph, salt or co-crystal. „„ Determination of the relative stability of different polymorphic forms. „„ Development of reliable procedures to prepare selected polymorphs.

Year 2009 was very important for Crysforma: With the extension of ICIQ facilities, the unit has now its own laboratory and thus is able to carry out a higher number of projects. In order to make the most of this increased capacity, Crysforma has modified its organization, appointing Dr Jordi Cerón as Unit Manager, while Dr Lluís Solà and Dr Jordi Benet-Buchholz keep collaborating closely with the unit as Scientific Advisors. In addition to this, Crysforma launched a campaign to incorporate European companies to its current client base. The first step was changing the name of the unit from Polymorphism R&D Unit to Crysforma and creating a brand image, including an independent website: www.crysforma.com

„„ Development of analytical methods for polymorph quantification. „„ Crystallization of compounds difficult to crystallize or formerly only known as amorphous solids. „„ Development and scale-up of robust crystallization procedures. „„ Resolution of chiral compounds by selective diastereomeric salt crystallization. „„ Crystallizations oriented to the preparation of single crystals and structure determination by single crystal X-ray diffraction.

95


4. PROJECTS Esteve-ICIQ Joint Unit

4.2 Esteve – ICIQ Joint Unit

Unit Manager: Dr. Félix Cuevas Project Researchers: Dr. Dani Font / Dr. Ana Isabel Oliva / Dr. Frédéric Ratel / Dr. Mª Ángeles Sarmentero Laboratory Technician: Josep Mª López Scientific Advisors: Prof. Pau Ballester / Prof. Antonio M. Echavarren / Prof. Miquel À. Pericàs

96

The Esteve – ICIQ Joint Unit is a collaborative research project between the Spanish pharmaceutical company  ESTEVE and ICIQ, dedicated to the development of new chemical processes to obtain chemically new scaffolds and building blocks that can generate new medicinal chemistry libraries with the aim to identify new lead compounds. It involves up to seven post-doctoral researchers and takes advantage of ICIQ group leaders’ assessment and of ICIQ’s state-of-the-art instrumentation facilities.


4. PROJECTS Joint Projects with Industry

4.3 Joint Projects with Industry

Framework

Company

Project

Scope

Total allocated

2009 Invoiced

 Heterogeneous Catalysis

Chemical

R+D

European

424.000 €

137.000 €

 Heterogeneous Catalysis

Chemical

R+D-Computational

European

132.600 €

67.600 €

 Homogeneous Catalysis

Chemical

R+D

European

438.000 €

67.000 €

 Homogeneous Catalysis

Chemical

R+D

European

244.100 €

34.050 €

 Homogeneous Catalysis

Chemical

R+D

European

141.600 €

63.600 €

 Homogeneous Catalysis

Pharmaceutical

R+D

Catalan

197.000 €

60.000 €

 Homogeneous Catalysis

Pharmaceutical

R+D

Catalan

107.000 €

75.000 €

 Homogeneous Catalysis

Pharmaceutical

R+D

Catalan

1.260.000 €

330.000 €

 Homogeneous Catalysis

Pharmaceutical

R+D-Computational

European

53.000 €

Invoiced in 2008

 Homogeneous Catalysis

Pharmaceutical

R+D

Spanish

18.000 €

9.000 €

 Homogeneous Catalysis

Chemical

R+D

Spanish

37.500 €

6.250 €

 Photovoltaics

Renewable Energy

R+D

Spanish

270.000 €

90.000 €

 Photovoltaics

Renewable Energy

R+D

Spanish

70.000 €

35.000 €

 Solid state development

Pharmaceutical

R+D

Spanish

65.000 €

16.250 €

 Solid state development

Pharmaceutical

R+D

Catalan

62.000 €

62.000 €

 Solid state development

Pharmaceutical

R+D

Catalan

425.400 €

237.180 €

 Solid state development

Pharmaceutical

R+D

Catalan

258.744 €

258.744 €

 Solid state development

Pharmaceutical

R+D

Catalan

46.550 €

46.550 €

97


4. PROJECTS Patents

4.4 Patents Copyright

T-263-05

Status

Title

cLab (Computational Laboratory Web Manager)

Inventors

Carles Bo, Joan Iglesias, José C. Ortiz

Granted

Application Date

21/07/05

cLab, a web portal to access, use and manage computational resources A computational laboratory is a high performance supercomputing centre based on heterogeneous computer resources. cLab is an internet-based application that allows users to manipulate files and folders, prepare computational tasks, submit and control them while they are running, as well as visualize or store results. Perfectly integrated to Linux and adaptable to different external queuing systems, cLab provides tools for the users as well as for the system administrator.

Patent Ref.

US60/833.069

Status

Processing

Application Date

Title

Compound and Method for the selective extraction of higher fullerenes from mixtures of fullerenes

Inventors

Javier de Mendoza, Elisa Huerta, Gerald Metselaar

24/07/07

Cost-effective method for the selective extraction and purification of high order fullerenes (>C70) based on a novel extracting agent Progress in the chemistry of higher fullerenes suffers from the limited availability of these compounds. Extraction methods for these compounds are based or include chromatography in some step of the process, making them expensive and time-consuming. The developed method is straightforward, performs under mild conditions and is based on simple solid-liquid extractions. High yields are obtained and no further purification step is required.

Patent Ref.

EP06380268.0

Status

Granted

Application Date

17/10/06

Title

Bis-diglycolamides (BISDGA) as new extractants for lanthanides [LN(III)] and actinides [AN(III)] from aqueous high-level wastes

Inventors

Javier de Mendoza, M. Teresa Murillo, Jorge Sánchez, Marta Almaraz, Amparo González, Giuseppe Modolo, Pilar Prado

Novel compounds and method for the selective extraction of actinides and lantanides Novel compounds and an extraction method were developed for the removal of An (III) and Ln (III) from nitric aqueous solutions, in particular from liquid radioactive residues coming from nuclear waste residues treatment. The compounds show optimal extraction capacity, high hydrolytic and radiolytic stability, as well as higher selectivity and performance compared with alternative compounds. Moreover, the short contact times required make them very susceptible for large scale applications.

98


4. PROJECTS Patents

Patent Ref.

US60/971.779

Title

Cycloaddition of azides and alkynes

Inventors

Steve Nolan, Silvia Díez

Status

Processing

Application Date

12/09/07

Novel versatile and highly efficient catalysts for the obtention of 1,2,3-triazoles under mild conditions. “Click Chemistry” is a chemical philosophy inspired in the way nature generates substances by joining small modular units. This catalytic system fulfills all the requirements of Click Chemistry, that is: Mild and convenient reaction conditions, in water or solvent-free and simple isolation of products with no purification step. Very high reaction rates and excellent yields can be obtained with these catalysts. Additionally, the reaction is not only applicable to terminal but also to internal alkynes.

Patent Ref.

PCT/EP2007/055110

Status

Processing

Application Date

25/05/07

Title

Tri-tert-butylcarboxyphtalocy anines, uses thereof and a process for their preparation

Inventors

Emilio Palomares, Tomás Torres, Michael Graetzel

Novel compounds for the manufacture of Dye-Sensitized Solar Cells (DSSC) Compatible with roll-to-roll production and manufactured from cheap and non-toxic materials, DSSC provide a low cost alternative to silicon- based photovoltaics. Due to their technical characteristics, DSSC are ideally suited for building or textile integrated photovoltaics, and for the powering of personal electronic and stand-alone equipment. The developed compounds gather many desirable features: optical and chemical stability, solar light absorption efficiency, low aggregation and possibility of being anchored to polymeric and inorganic substrates.

99


4. PROJECTS Patents

Patent Ref.

PCT/EP2008/061264

Status

Title

New Phospine-Phosphite Ligands

Inventors

Anton Vidal-Ferran, Miquel Pericàs, Héctor Fernández

Processing

Application Date

07/09/07

Novel catalysts for the asymmetric hydrogenation of a wide range of unsaturated compounds. Asymmetric hydrogenation reactions are used in a wide variety of chemical processes, in particular, in the manufacture of pharmaceutical intermediates. The developed catalysts are reusable, highly stable, exhibit high reactivity and enantioselectivity and can be applied to a wide range of unsaturated compounds. They offer great substitution opportunities for varying the electronic and steric properties in order to adapt them to a specific substrate.

Patent Ref.

PCT/ES2009/070238

Status

Extention

Application Date

08/06/08

Title

Procedimiento de obtención de Fullerenos y Fullerenos así obtenidos

Inventors

Antonio M. Echavarren, José Ángel Martín Gago, Berta Gómez-Lor, Javier Méndez Pérez-Camarero, Maria Francisca López Fagundez, Renaud Caillard, Gonzalo Otero, Carlos Sánchez-Sánchez, Celia Rogero Blanco

Method for the highly specific production of fullerene derivatives and heterofullerenes Graphite vaporization provides an efficient, yet uncontrolled, method for the production of fullerenes. However, some fullerene derivatives or unusual fullerene species can only be produced using controlled synthesis methods. The method developed consists in placing predesigned polyaromatic precursors on a catalytically active metal surface, which is subsequently heated. The precursors lose hydrogen and close, forming the desired fullerene. In contrast with other methods, the yield is extremely high, nearly 100%.

Patent Ref.

EP09382121

Status

New Application

Application Date

24/07/09

Title

Tristriazoles as an effective ligand for copper catalyzed alkyne-azide cycloaddition reaction

Inventors

Miquel Pericàs, Salih Özçubukçu, Ciril Jimeno, Erhan Ozkal

Highly active catalyst for the “Click reaction” Novel catalysts for the Huisgen 1,3-dipolar cycloaddition af alkynes and azides have been developed. These catalysts, based on tris-triazole – Cu(I) structures, present several advantageous characteristics: fast reaction times at room temperature with low catalyst loadings, compatible with free amino groups, can be easily fine-tuned for specific applications and can be anchored to a polymeric support without losing activity.

Patent Ref.

EP0938227.0

Status

New Application

Application Date

Title

Process for the carboxylation of aryl halides with palladium catalysts

Inventors

Rubén Martín, Arkaitz Correa

14/10/09

Method of production of benzoic acids from aryl bromides and CO2 Because of its abundance, low cost and non-toxicity CO2 is regarded as a highly interesting carbon source. The developed method yields benzoic acids (which are important motifs in many natural and medicinal products) from Pdcatalyzed carboxylation of aryl bromides with CO2. Compared with other methods, this one avoids the high toxicity associated with the use of CO and does not require the synthesis of organometallic reagents.

100


5

Education and Scientific Outreach D

uring the year 2009, the scientific activity carried out at our institution has been intense. Weekly seminars have

been celebrated, with the participation of renowned professors and scientists from around the world. Besides, the Institute has also organized the fourth edition of the ICIQ Summer School of Organometallic Chemistry. Its scientific program included a number of lectures given by world-class experts in organic, inorganic and organometallic chemistry. As a part of the 2009 Science Week, ICIQ has organized a broad set of activities, such as daily visits for secondary education students, an open workshop of chemical experiments entitled ”Química en família” —especially oriented to children­—,

and the participation in the Fira de Mostres d’R+D in Tarragona with an interactive stand, where visitors could perform chemical experiments by themselves. On the other hand, we have continued with the ICIQ Fellowships Programmes (PhD and Summer Fellowships) which were set out in 2008. Moreover, the ICIQ participated for the first time in the programme Joves i Ciència organised by

Obra Social de Caixa Catalunya , and the ICIQ/URV Master in Synthesis and Catalysis has started the present academic year 2009/2010.

101


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Seminars Programme

5.1 ICIQ Seminars Programme

102

Date

Speaker

University/Centre

Seminar

9 Jan. 2009

Prof. Emilio Palomares

Institut Català d'Investigació Química, Tarragona (Spain)

Molecular Photovoltaics: From Chemistry to Devices

16 Jan. 2009

Prof. F.Ekkehardt Hahn

Anorganisch-Chemisches Institut der WWU Münster (Germany)

N-Heterocyclic carbenes as building block for macrocyclic ligands and supramolecular assemblies

23 Jan. 2009

Prof. Michel Etienne

Université Paul Sabatier, Toulouse III (France)

CH and CC agostic interactions: Structural and mechanistic studies of strong CX bond activation

29 Jan. 2009 

Prof. Peter Chen

Eidgenössische Technische Hochschule, Zürich (Switzerland)

Ruthenium, rhenium, and gold carbenes

6 Feb. 2009 

Prof. Bernd Plietker

Institut für Organische Chemie, Universität Stuttgart (Germany)

Recent advances in sustainable metal catalysis

10 Feb. 2009 

Dr. José Ramón Galán

Universidad de Valencia (Spain)

Multifunctional molecular materials: From simple design to complex (nano?) structures


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Seminars Programme

Date

Speaker

University/Centre

Seminar

27 Feb. 2009 

Prof. Armido Studer

Westfälische WilhelmsUniversität Münster (Germany)

Functionalized cyclohexadienes and nitroxides in organic synthesis

6 Mar. 2009 

Prof. Paul C. J. Kamer

The Edinburgh and St. Andrews Research School of Chemistry, Edinburgh (UK)

Ligand design in homogeneous catalysis: Rational design, combinatorial approaches, and artificial enzymes

10 Mar. 2009 

Prof. Paolo Melchiorre

University of Bologna (Italy)

Asymmetric aminocatalysis: After the gold rush

19 Mar. 2009 

Prof. Lutz Ackermann

Institut für Organische und Biomolekulare Chemie, Georg-August-Universitaet Goettingen (Germany)

Modern arylation reactions: From air-stable preligands to catalytic C-H bond functionalizations

2 Apr. 2009 

Prof. Luis M. Liz-Marzán

Universidad de Vigo (Spain)

Morphology control of noble metals in the nanoscale

17 Apr. 2009 

Dr. Paul W. Davies

University of Birmingham (UK)

New and old reactions by noble metal catalysis

20 Apr. 2009 

Dr. Brian C. O'Regan

Imperial College London (UK)

Understanding the chemistry of dye sensitized solar cells

24 Apr. 2009 

Prof. Christoph Andreas Schalley

Institut für Chemie und Biochemie der Freien Universität Berlin (Germany)

Mass spectrometry of non-covalent complexes: Structure, reactivity and dynamics

6 May 2009 

Dr. Neil Robertson

University of Edinburgh (UK)

Light-harvesting dyes for solar energy – Can coordination chemistry save the world?

15 May 2009 

Prof. Santiago Álvarez

Universitat de Barcelona (Spain)

Molecular and supramolecular structures: a treasure of polyhedral shapes and intriguing symmetries

22 May 2009 

Prof. Frank E. McDonald

Emory Univesity, Atlanta (USA)

Fumonisin: A template for methodology development and for drug discovery

28 May 2009 

Prof. Dirk Trauner

Ludwig-MaximiliansUniversität München (Germany)

Building molecules to tackle cancer and blindness

5 Jun. 2009 

Prof. Franc Meyer

Georg-August-Universität Göttingen (Germany)

(YOUNG RESEARCHERS SEMINAR): Cooperating metal centers: metalloenzyme active sites, bioinspired catalysis, and beyond

12 Jun. 2009 

Dr. José M. Lassaletta

Instituto de Investigaciones Químicas (CSIC-Us), Sevilla (Spain)

Nuevos ligandos quirales basados en nitrógeno, carbono y azufre. Diseño, síntesis y aplicaciones en catalisis asimétrica

15 Jun. 2009 

Prof. Luis A. Echegoyen

Clemson University, South Carolina (USA)

Buckyball maracas: Synthesis, functionalization and electronic properties of endohedral fullerenes

22 Jun. 2009 

Prof. Claudio Palomo

Universidad del País Vasco (Spain)

Stoichiometric and catalytic asymmetric synthesis: new examples

26 Jun. 2009 

Prof. Jérôme Lacour

Université de Gèneve (Switzerland)

Ionic interplay in asymmetric synthesis and catalysis

103


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Seminars Programme

104

Date

Speaker

University/Centre

Seminar

3 Jul. 2009 

Prof. Christophe Coperet

Université de Lyon, Institut de Chimie de Lyon (France)

(YOUNG RESEARCHERS SEMINAR) Molecular design of heterogeneous catalysts

16 Jul. 2009 

Prof. Doug Grotjahn

San Diego State University (USA)

Proton tansfer and hydrogen bonding in organometallic structure and catalysis

10 Sept. 2009  Prof. Benjamin List

Max-Plank-Institut für Kohlenforschung (Germany)

A small molecule with a big impact: Inspirations from proline catalysis

18 Sept. 2009  Prof.Frank Glorius

Universität Münster (Germany)

N-Heterocyclic carbenes in catalysis and other efficient reactions

25 Sept. 2009  Prof. Javier Pérez-Ramirez

Institut Català d'Investigació Química-ICIQ, (Tarragona, Spain)

Demand more on your catalyst - Engineering hierarchical Zoelites

16 Oct. 2009 

Dr. Arjan Kleij

Institut Català d'Investigació Química-ICIQ, (Tarragona, Spain)

Metallosalens as versatile components of functional materials: Multinuclear structures, supramolecular synthesis and homogeneous catalysis applications

23 Oct. 2009 

Prof. José Luis Serrano

Facultad de Ciencias - ICMA INA, Zaragoza (Spain)

Different approaches to new materials by using liquid crystalline phases

30 Oct. 2009 

Prof. Manfred T. Reetz

Max-Planck-Institut für Kohlenforschung, (Germany)

Directed evolution of enantioselective enzymes: An unceasing source of catalysts

13 Nov. 2009 

Prof. Jonathan P. Clayden

The University of Manchester (UK)

Conformational communication and new organolithium reactivity

20 Nov. 2009 

Prof. Magnus Rueping

Johann Wolfgang GoetheUniversity, Frankfurt am Main (Germany)

Chiral brønsted acids in asymmetric catalysis

11 Dec. 2009 

Prof. Andreas Kirschning

Leibniz Universität Hannover (Germany)

Enabling technologies in organic chemistry- from minireactors to new heating techniques

15 Dec. 2009 

Prof. Koichiro Oshima

Kyoto University (Japan)

Pd-Catalyzed selective reactions utilizing tertiary unsaturated alcohols

18 Dec. 2009 

Dr. Natalie Fey

University of Bristol (UK)

(YOUNG RESEARCHERS SEMINAR): Exploring ligand effects in homogeneous catalysis - Maps, models and mechanisms


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Summer School

5.2 ICIQ Summer School

Directors

Scientific Program: Speakers

Prof. Miguel Ángel Sierra (Universidad Complutense de Madrid)

Prof. M. Christina White (University of Illinois) 1. C-H As A New Functional Group: Discovery of Predictably Selective Reactions 2. C-H As A New Functional Group: Streamlining Synthesis

Prof. Antonio M. Echavarren (Institut Català d’Investigació Química, ICIQ)

Prof. Patrick Walsh (University of Pennsylvania) 1. Asymmetric C-C and C-O Bond-Forming Reactions 2. New Bifunctional Reagents for Tandem Reactions Prof. Alexandre Alexakis (Université de Gèneve) 1. Copper Catalyzed Asymmetric Transformations: Conjugate Addition and Allylic Substitution. Part 1 2. Copper Catalyzed Asymmetric Transformations: Conjugate Addition and Allylic Substitution. Part 2 Prof. Phil Baran (The Scripps Research Institute) 1. Case Studies in Chemoselective Synthesis. Part 1 2. Case Studies in Chemoselective Synthesis. Part 2 Prof. Tomislav Rovis (Colorado State University) 1. Catalytic Generation and Interception of Metalacycles 2. Chiral Nucleophilic Carbenes in Organic Synthesis: Catalyst Development and Synthetic Applications Prof. Carsten Bolm (RWTH Aachen University) 1. Iron Salts in Metal Catalysis 2. New Ligands fo Enantioselective Metal Catalysis Prof. Christina Moberg (KTH School of Chemical Science and Eng.) 1. Interelement Compounds as Efficient Synthetic Tools 2. Acetylcyanation of Carbonyl Compounds – Improved Enantioselection via Minor Enantiomer Recycling Prof. Jay S. Siegel (University of Zurich) 1. Dynamic and Topological Stereochemistry. 2. Polar-pi Effects. Benzene Dimers to Silyl Cations. Prof. Juan Carlos Carretero (Universidad Autónoma de Madrid) 1. Recent Applications of Ferrocene Ligands in Asymmetric Catalysis 2. Coordinating Sulfonyl Groups in Metal-Catalyzed Reactions

105


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Fellowships Program

5.3 ICIQ Fellowships Programme Summer Fellowships Programme

PhD Fellowships Programme

ICIQ Summer Fellowships are an excellent opportunity to learn, work and live in a challenging environment of cutting-edge research under the supervision of distinguished scientists.

The Institute of Chemical Research of Catalonia offered a joint call of PhD Fellowships in the following projects:

Outstanding undergraduate students with a background in Chemistry or related studies are encouraged to apply to these Summer Fellowships, which consist of a three-month paid internship in one of ICIQ’s research groups during the months of July, August and September. This year 2009, ICIQ has awarded ten candidates from different countries (Spain, United Kingdom, Italy, US and Colombia), which had the oportunity to carry out several research projects in some of the groups of the centre.

„„ "Hierarchical Zeolites as Efficent Supports for Metal Species and Enzymes" (Dr. Javier Pérez-Ramírez)

„„ "Supported Ligands and Catalysts for Asymmetric Catalysis��� (Prof. Miquel A. Pericàs)

„„ "Catalysts for Artificial Photosynthesis" (Prof. Antoni Llobet)

„„ "Selectivity in Chemical Processes on Heterogeneous Catalysis” (Dra. Núria López)

„„ "New Organic Material and Molecules for Efficient Molecular Photovoltaic Devices” (Dr. Emilio Palomares) „„ "New Gold-catalyzed Reactions” (Prof. Antonio M. Echavarren) „„ "Palladium and Gold-catalyzed Methods for the Synthesis of Open Fullerenes” (Prof. Antonio M. Echavarren) „„ "Design, Preparation and Catalytic Studies of P-OP Ligands in Metal-mediated Asymmetric Transformations” (Dr. Anton Vidal)

106

„„ "Computational Modeling of Enantioselective Catalysis” (Prof. Feliu Maseras) „„ "Supramolecular Approaches to Catalysis” (Prof. Pablo Ballester) „„ "Computational Design of Small-molecule Catalysts” (Prof. Carles Bo) „„ "Supramolecular Catalysts for Hydroformylation” (Prof. Piet W. N. M. van Leeuwen) „„ "Dynamic Multivalency for the Recognition of Protein Surfaces” (Prof. Javier de Mendoza)


5. EDUCATION and SCIENTIFIC OUTREACH Master inSynthesis and Catalysis

5.4 Master in Synthesis and Catalysis The ICIQ/URV Master in Synthesis and Catalysis teaches students about: the design of chemical processes in industry and the laboratory, environmental and economic factors; the design of new methods of synthesis using catalysts; the drawing up of applied research proposals; and the study of design,  preparation, characterization, recovery, deactivation and regeneration of catalysts. This Master started the present academic year 2009/2010, and there were 20 available places.

Professors: „„ Carmen Claver (URV) „„ Miquel A. Pericàs (ICIQ) „„ Piet van Leeuwen (ICIQ) „„ Antonio M. Echavarren (ICIQ) „„ Gabriel González (ICIQ) „„ Pau Ballester (ICIQ) „„ Noemí Cabello (ICIQ) „„ Feliu Maseras (ICIQ) „„ Montse Diéguez (URV) „„ Maribel Matheu (URV) „„ Òscar Pàmies (URV) „„ Carles Bo (ICIQ) „„ Yolanda Cesteros (URV) „„ Mar Reguero (URV) „„ Javier Pérez-Ramírez (ICIQ) „„ Pilar Salagre (URV) „„ Rubén Martín (ICIQ) „„ Elena Fernández (URV) „„ Yolanda Díaz (URV) „„ Marta Giménez (URV)

Coordinators: „„ Prof. Carmen Claver (URV) „„ Prof. Antonio M. Echavarren (ICIQ)

107


5. EDUCATION and SCIENTIFIC OUTREACH Dissemination Activities

5.5 Dissemination Activities Events

108

Title

Type / Framework

Organizer/s

Location

Date

MIT European Career Fair

Recruiting Fair

MIT

Boston (USA)

24 – 26 Jan. 2009

Saló de l’Ensenyament

Education Exhibition

Fira Barcelona

Fira Barcelona

18 Feb. – 22 Mar. 2009

Fem un parèntesi a la Química

Seminar

ICIQ

ICIQ

Throughout 2009

ACHEMA (ICIQ and Crysforma)

Trade Exhibition

Messe Frankfurt GmbH

Frankfurt (Germany)

11 – 15 May 2009

Fira Laboral UB

Recruiting Fair

UB

Barcelona

14 May 2009

ICIQ’s 5th Anniversary International Symposium

Symposium

ICIQ

ICIQ (Tarragona)

17 Jun. 2009

ICIQ’s Phase II Inauguration

Inauguration

ICIQ

ICIQ (Tarragona)

19 Jun. 2009

Summer School

Summer School

ICIQ

ICIQ (Tarragona)

20 – 24 Jul. 2009

Fòrum Tecnio

Trade Meeting

Acc10

Barcelona

21 Jul. 2009

Trends in Nanotechnology

International Conference

Phantoms Foundation

Barcelona

07 – 11 Sep. 2009

CPhI – ICSE (Crysforma)

Trade Exhibition

UBM International Media

Madrid

13 – 15 Oct. 2009

Guided visits at ICIQ

Setmana de la Ciència

ICIQ

ICIQ (Tarragona)

16 – 20 Nov. 2009

Fira de Mostres d’R+D

Science Week 09

URV

Campus Catalunya URV (Tarragona)

18 – 20 Nov. 2009

Química en Família

Workshop Science Week 09

ICIQ

ICIQ (Tarragona)

19 Nov. 2009

Química en Família

Workshop Science Week 09

ICIQ

CaixaForum Tarragona

21 Nov. 2009


5. EDUCATION and SCIENTIFIC OUTREACH Dissemination Activities

Journals / Magazines

Newspapers

Media

Title

Date

Teraflop Scope: Local

"La catàlisi heterogènia i la química computacional"

Oct.2009

Presència (El Punt) Scope: Regional

"ICIQ- solucions sostenibles i menys costoses"

8 Nov. 2009

Media

Title

Date

ADN Scope: National

"Ampliación Instituto Catalán Investigaciones Quimicas ha costado 16 millones"

19 Jun. 2009

Crònica Scope: Regional

"L'ICIQ estrenarà les noves instal.lacions el mes de juny"

June 2009

Diari de TGN Scope: Regional

"Un viaje al centro de la ciencia"

11 Dec. 2009

"José Montilla inaugura hoy la ampliación del ICIQ"

19 Jun. 2009

"Cambrils acull una trobada de científics que pretenen transformar els components de l'aigua en un combustible renovable"

01 Apr. 2009

“Nuevas instalaciones del ICIQ”

17 May 2009

"Se establecerán sinergias entre investigadores y empresas”

23 May 2009

“Un membre de l’ICIQ a Tarragona descobreix com estabilitzar un important supressor tumoral”

16 Jun. 2009

"El president Montilla inaugura la ampliación de los laboratorios del Institut Català d'Investigació Química"

20 Jun. 2009

"Miquel Pericàs director del ICIQ"

20 Jun. 2009

"La ampliación del ICIQ atraerá a 100 científicos del todo el mundo"

20 Jun. 2009

"La URV inviste como Doctor Honoris Causa al químico Piet van Leeuwen"

14 Oct. 2009

"Detrás de cada objeto hay un proceso químico"

24 Oct. 2009

"Química en família"

21 Nov. 2009

Diario de Teruel Scope: Local

"Jornadas abiertas Consolider-Intecat"

28 Oct. 2009

Diario médico Scope: National

"Diseñan una sustancia que bloquea canales de potasio de membranas celulares"

05 May 2009

El País Scope: National

”Un programa para fichar a los cientifícos con más talento"

24 May 2009

El Punt Scope: Regional

"Partir l'aigua per moure el món"

07 Apr. 2009

"El primer químic "honoris causa" aposta per abaratir l'energia a partir de nous materials"

15 Oct. 2009

"Medalla Narcís Monturiol a l'ICIQ i al catedràtic de la URV Francesc Xavier Rius"

17 Dec. 2009

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5. EDUCATION and SCIENTIFIC OUTREACH Dissemination Activities

Newspapers

Media

Title

Date

Indicador Scope: Regional

"A la recerca d'un nou combustible fòssil"

May 2009

La Malla Scope: Regional

“L'Institut Català d'Investigacions Químiques es consolida"

22 Jun. 2009

La Vanguardia Scope: National

"El ICIQ impulsa CRYSFORMA para dar soporte a la industria farmacéutica en el desarrollo del estado sólido de fármacos"

26 Feb. 2009

"Ciencia de primera"

27 Feb. 2009

"La catálisis es la actividad clave para una química sostenible"

13 Jul. 2009

"La Generalitat reordena el mapa de la innovación en Catalunya"

28 Dec. 2009

"La fórmula del futur"

06 Feb. 2009

"L'Institut Català d'Investigació Química de Tarragona completa al juny la segona fase de les seves instal.lacions"

11 May 2009

"Montilla assegura que la recerca i la innovació són els elements clau per reactivar l'economia del país"

19 Jun. 2009

"Europa premia vuit joves investigadors de Catalunya"

17 Sep. 2009

"Científics europeus debaten a Cambrils com separar oxigen i hidrogen"

02 Apr. 2009

"L'ICIQ és sinònim d'investigació d'excel.lència al servei de la societat"

30 Oct. 2009

"Un catedràtic de la URV i l'ICIQ reben la medalla Narcís Monturiol"

17 Dec. 2009

Reus digital Scope: Local

"Diversos científics pretenen transformar l'aigua en un combustible renovable"

02 Apr. 2009

Tarragona municipal Scope: Local

"S'inaugura l'ampliació de l'ICIQ"

July 2009

Media

Title

Date

Radio Tarragona Scope: Regional

"L'ICIQ inaugura la segona fase d'ampliació amb l'objectiu de consolidar-se com a centre de referència a Europa"

19 Jun. 2009

Media

Title

Date

Info K (TV3) Scope: Regional

"Experiments casolans"

20 Nov. 2009

TeleNotícies comarques (TV3) Scope: Regional

"Nous laboratoris que busquen energies alternatives"

19 Jun. 2009

TeleNotícies migdia (TV3) Scope: Regional

"El president Montilla inaugura la segona fase de l'Institut Català d'Investigació Química"

19 Jun. 2009

Europa press Scope: Regional

"Tarragona pone en marcha la ampliación del Instituto Catalán de Investigaciones Químicas"

19 Jun. 2009

L'Avui Scope: Regional

Més Tarragona Scope: Local

110

Radio

TV media


5. EDUCATION and SCIENTIFIC OUTREACH ICIQ Newsletter

Joves i Ciència Programme ICIQ participates in the program Joves i Ciència (Young People and Science Programme) organised by Obra Social de Caixa Catalunya with the aim to encourage and motivate young students in the field of Science. ICIQ's participation in this programme consists of being active in the E2C3 Summer Workshop and hosting students in its labs to let them take part in research projects. This Summer, scientists from Prof. Palomares research group have lead the project Solar Energy in the E2C3 Summer Workshop. In this workshop, students learn how to build solar cells that transform sunlight into electric energy using natural pigments extracted from plants. On the other hand, Prof. Palomares lab at ICIQ hosted two students which learned how to build hybrid leds and solar cells.

5.6 ICIQ Newsletter The ICIQ Newsletter was first published in the middle of 2009 as a new communication tool, especially oriented to old ICIQ members and to the external public. Thus, besides the publication of purely scientific news, the Newsletter aims to inform from a closer point of view about the daily life at ICIQ, with the hope to enhance the feeling of unity among the members working in our institution. The Newsletter is thought to be published every three months approximately, and at the end of the year 2009 there were 61 subscribers.

111


112


Appendix I Board of Trustees. & Scientific Advisory Board Board of Trustees

Scientific Advisory Board

President

„„ Prof. George M. Whitesides Harvard University, USA

„„ Honourable Mr. Josep Huguet i Biosca, Minister for Innovation, Universities and Enterprise of the Government of Catalonia.

Vice President „„ Excm. and Magfc. Mr. Francesc Xavier Grau i Vidal, Vice-Chancellor of the University Rovira i Virgili.

Members „„ Mr. Joan Roca i Acín, General Director of Research. „„ Mr. Joan Majó i Roca, Universities and Research Commissioner. „„ Mr. Jesús Loma Osorio Blanch (BAYER POLÍMEROS, S.L.) „„ Mr. Luís Cabra Dueñas (REPSOL YPF, S.A.) „„ Mr. Joan Mª García Girona (BASF ESPAÑOLA S. A.) „„ Mr. Antoni Esteve i Cruella (LABORATORIS ESTEVE, S.L.)

„„ Prof. Ernesto Carmona Instituto de Investigaciones Químicas Isla de la Cartuja, Universidad de Sevilla-CSIC, Spain „„ Prof. Julius Rebek, Jr.  The Scripps Research Institute, USA „„ Prof. Avel·lí Corma  Institut de Tecnologia Química, CSIC-Universitat Politècnica de València, Spain „„ Prof. Stephen L. Buchwald  Massachusetts Institute of Technology, USA „„ Prof. Luís Oro Universidad de Zaragoza, Spain „„ Prof. Andreas Pfaltz  University of Basel, Switzerland „„ Prof. Jeremy K. M. Sanders Cambridge University, UK „„ Prof. Erick M. Carreira ETH Zentrum, Zürich, Switzerland „„ Prof. Michael Graetzel Ecole Polytechnique de Lausanne, Switzerland „„ Prof. José Barluenga Instituto Universitario de Investigación Enrique Moles, Universidad de Oviedo, Spain

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Appendix II Staff Distribution Management and Strategic Area

Research Groups

Research Support Area

Total

114


Appendix III 5-Year Evaluation 2009 SCIENTIFIC EVALUATION: ICIQ Quinquennial Evaluation 2004 – 2009 June 17 – 19, 2009 Tarragona, Spain

Evaluation committee: „„ Prof. Julius Rebek, Jr. (The Scripps Research Institute, USA) „„ Prof. Stephen L. Buchwald (Massachusetts Institute of Technology, USA) „„ Prof. Andreas Pfaltz (University of Basel, Switzerland) „„ Prof. Erick M. Carreira (ETH-Zurich, Switzerland) „„ Prof. Ernesto Carmona (Universidad de Sevilla-CSIC, Spain) „„ Prof. Luis Oro (Universidad de Zaragoza, Spain) „„ Prof. Jeremy K. M. Sanders (Cambridge University, UK) „„ Prof. Michael Graetzel (EPFL, Switzerland)

General Assessment of ICIQ A number of developments at ICIQ have taken place that are in line with its mission to maintain an emphasis on cutting edge research in the chemical sciences. These will ensure the Institute maintains its competitiveness in various critical disciplines and continue to maintain high visibility and scientific impact. These can be identified at various levels throughout the institution. In 2009 additional facilities have been completed with the capacity to house new research programs. Furthermore, resources have been secured to set up spin-off companies in the Science and Technology Park of Tarragona. The addition of Professor Michael Graetzel to Ecole Polytechnique de Lausanne, Switzerland to the Advisory Committee underscores the importance of chemistry as an enabling science that can address pressing problems in energy and nanotechnology with sustainable solutions. The introduction of a Tenure Track program is another welcome development, and two tenure track positions will be filled in the near future. Synergies with Universitat Rovira i Virgili will culminate in the inauguration of a masters program in synthesis and catalysis in 2009/2010. Examination of a number of various bibliometric parameters reveals that the scientific output remains excellent in quality and quantity. Scientific publications have appeared in top tier journals such as Nature, Angew. Chem., Proceedings of the

National Academy of Sciences (USA), and J. Am. Chem. Soc. During the previous five years publications from ICIQ have been cited a total of 5,789 times; the average citation per publication is 12.45 and the institutional h-factor equals 36. In 2008 the total number of citations was approximately 2400, and analysis of the mid-year status suggests this number will be significantly exceeded in 2009. ICIQ also has favorably positioned itself as an institution of higher learning, offering doctorates in chemistry, and soon a masters degree. The program sponsors numerous scholarly activities to the benefit of its students and the community at large. Weekly seminars provide the opportunity for members of the Institute to interact and engage in discussion with renowned researchers from industry (chemical and pharmaceutical) and academia. The speakers originate from leading institutions in Europe, North America, and Asia. The ICIQ Summer School of Organometallic Chemistry is a focused forum that enables exchange of the latest scientific developments in organic, inorganic, and organometallic chemistry. In 2008, ICIQ organized a range of activities and workshops for students from secondary schools to promote chemistry. A fellowship program has been established that enables outstanding undergraduates to spend a three-month paid internship at ICIQ. The Institute enjoys a healthy level of funding from a diverse portfolio of sources. This includes grants from the European Union (VI and VII Framework Programs), the Ministry of Science and Innovation (Consolider-Ingenio 2010, Programa PSE, Proyectos I+D), and Agencia de Gestió d’ajuts Universitaris I de Recerca (Ajuts per a GRUPS DE RECERCA). Numerous collaborative projects with industry have been established with regional, European and international firms involving pharmaceuticals, chemical and energy sectors. These cover disciplines in which the Institute enjoys recognition, such as homogeneous and heterogeneous catalysis, synthesis, and photovoltaics. A key feature of the present and future success of ICIQ is the tenure-track system in which young investigators are recruited internationally and are able to develop independent research careers. This contrasts favorably with the conventional career path in Spain. In the short term the ICIQ approach is leading to a stronger and more diverse scientific landscape, and in the longer term it will contribute to wealth creation and a more competitive economy. In summary the members of the Institute should be congratulated for having established a world-class research institution in a short period of time. We applaud the leadership and untiring efforts to the director, Prof. Miquel Pericas. ICIQ is well-positioned to count itself among the top research institutions in chemistry for the foreseeable future.

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AVALUACIÓ ADMINISTRATIVA: Comitè Avaluador:

2. Àrea de Gestió

„„ Dra. Montserrat Baucells Directora dels Serveis Científicotècnics-UB

2.1. Fortaleses ��„ Eficiència en les tasques desenvolupades.

„„ Dra. Margarida Corominas Directora de Gestió Institut de Recerca Biomèdica de Barcelona

„„ Estructura no sobredimensionada. Creixement en consonància al creixement de l’ICIQ.

„„ Sra. Iolanda Font de Rubinat Subdirectora general de Recerca

„„ Equip estable, amb membres clau presents des de l’inici de l’Institut.

„„ Dr. Ramon Moreno Director del Programa de centres de recerca (CERCA)

„„ Es percep com l’àrea més consolidada, segurament pel fet d’haver estat la primera en implementar-se.

„„ Dra. Carme Verdaguer Directora General Fundació Bosch i Gimpera „„ Dr. Eduard Valentí Director d’operacions d’R+D de Laboratoris Dr. Esteve

1. Organització General de l’ICIQ 1.1. Fortaleses „„ Estabilitat en la direcció del centre. „„ L’equip directiu composat pel Director, Directora Administrativa i Responsable de l’Àrea de Suport a la recerca es percep com un equip alineat i en sintonia.

2.2. Debilitats „„ Manca d’una unitat específica de Recursos Humans que incorpori funcions relacionades amb la gestió del personal en un sentit ampli. „„ Manca una anàlisi més detallada de les dades de l’activitat que sigui útil tant per a la presa de decisions com per a l’elaboració de la memòria. 2.3. Propostes de millora „„ Aprofundir en l’anàlisi dels costos totals per cada grup de recerca i unitat de suport.

„„ Preocupació i aposta per l’excel·lència en tots els nivells.

„„ Potenciar la informatització dels resultats i activitats de recerca.

„„ Pla estratègic integrat en la cultura de l’organització.

„„ Promoure un programa d’activitats de cohesió interna.

„„ Capacitat de reestructuració en funció de l’increment i la diversificació de l’activitat de l’Institut.

3. Àrea de Desenvolupament Tecnològic (Crysforma)

„„ L’ICIQ ha crescut de forma mesurada i ordenada.

„„ Existència d'un know-how únic i molt potent.

„„ Perfils professionals molt clars de les persones respecte als llocs de treball i funcions que desenvolupen, amb un alt nivell de motivació en totes les àrees.

„„ Equipament altament especialitzat i punter.

„„ Preocupació per la formació contínua del personal de totes les àrees.

3.1. Fortaleses

„„ Certificació de qualitat, important donada la vocació empresarial de la unitat. 3.2. Debilitats

1.2. Debilitats

„„ Poca estructura comercial per optimitzar els ingressos.

„„ Tres àrees depenen directament del Director de l’Institut: àrea de recerca, àrea estratègica i àrea de desenvolupament tecnològic.

„„ Probablement cal un reforç de l'assegurament de la confidencialitat.

„„ Manca de definició de les funcions de coordinació i promoció docent en l’organigrama de l’ICIQ. 1.3. Propostes de millora „„ Crear un manual o reglament de funcionament de l’organització que contempli l’organigrama. Repensar l’organigrama ponderant les responsabilitats i les funcions de cada àrea „„ Repensar la participació de les empreses a l’ICIQ (Consell Empresarial, Patronat i Unitats Mixtes). No sembla necessari que les empreses del Consell contractin o facin donacions a l’ICIQ.

„„ Presència en l'equip de persones a temps complet i d'altres a temps parcial. 3.3. Propostes de millora „„ Avaluació integral del compte de resultats de Crysforma, estudiant els costos totals. „„ En el moment actual sembla adequat fer un pla d'empresa per avaluar si interessa crear una empresa spin-off (incloent un estudi del mercat potencial a nivell internacional). „„ Si es decideix crear una spin-off hi ha d'haver una clara separació entre aquesta i l'ICIQ (a nivell de personal i equipament). „„ Aquesta àrea no té estructura, pel que a nivell de l'organigrama podria formar part de l'àrea Estragègica.

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Appendix IV Funding Evolution Percentage of competitive income over the total ICIQ funds

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Appendix V PhD Thesis

118

Name:

Elena Herrero Gómez

University: Universitat Rovira i Virgili (URV)

Date Defense:

10th July, 2009

Supervisor/s:

Prof. Antonio M. Echavarren / Prof. Feliu Maseras

Title:

Gold(I)-catalyzed cyclizations of 1,6- and 1,7-enynes: New gold complexes and cyclopropanation reactions

Cometee:

Prof. Nazario Martín (Universidad Complutense de Madrid) / Prof. Louis Fensterbank (Université Paris VI) / Prof. Gregori Ujaque (Universitat Autònoma de Barcelona) / Prof. Carmen Claver (Universitat Rovira i Virgili) Prof. Miquel A. Pericàs (ICIQ)

Name:

Héctor Fernández Pérez

Date Defense:

1st September, 2009

Supervisor/s:

Prof. Anton Vidal

Title:

Towards Highly Efficient Ligands for Asymmetric Hydrogenations: a Covalent Modular Approach and Investigation into Bio-inspired Supramolecular Strategies

Cometee:

Prof. Asunción Barvero (Universidad de Valladolid) / Prof. José Daniel Carmona (CSIC-Universidad de Zaragoza) / Prof. Antonio Pizarro (CSIC-Universidad de Sevilla) / Prof. Carmen Claver (Universitat Rovira i Virgili) Prof. Miquel A. Pericàs (ICIQ)

Name:

Guzmán Gil Ramírez

Date Defense:

19th November, 2009

Supervisor/s:

Prof. Pau Ballester

Title:

Supramolecular Chemistry of Aryl Extended Calix[4]Pyrroles

Cometee:

Prof. Javier de Mendoza (ICIQ) / Prof. Antoni Costa (Universitat de les Illes Balears) / Prof. Nazario Martín (Universidad Complutense de Madrid) / Prof. Alberto Tárraga (Universidad de Murcia) / Prof. Juan R. Granja (Universidad de Santiago de Compostela)

University: Universitat Rovira i Virgili (URV)

University: Universitat Rovira i Virgili (URV)

Name:

Frédéric Ratel

Date Defense:

20 March, 2009

University: Universidad Autónoma de Madrid (UAM)

Supervisor/s:

Javier de Mendoza

Title:

Towards a combinatorial approach to supramolecular catalysis using hydrogen bonding driven substrate activation and anchoring.

Cometee:

Pilar Prados (Universidad Autónoma de Madrid) / Prof. Rosa Claramunt (UNED) / Prof. Pau Ballester (ICIQ) / Prof. Julio Álvarez (Universidad de Alcalá)

Name:

Vera Martos

Date Defense:

24th March, 2009

Supervisor/s:

Javier de Mendoza

Title:

Polycationic multivalency: Protein recognition and cell uptake via oligoguanidinium scaffolds

Cometee:

Prof. Cecilio Giménez (Universidad Autónoma de Madrid) / Prof. Ernest Giralt (Universitat de Barcelona) / Prof. Fernando Albericio (Universitat de Barcelona) /Dr. Jesús Jiménez (CSIC - Madrid)

University: Universidad Autónoma de Madrid (UAM)



Memoria Científica ICIQ 2009