south europe-japan joint forum inorganic chemistry and its
TRANSCRIPT
InorganicChemistry andits InterfacesOctober 17-18, 2014
Collège Doctoral EuropéenUniversité de Strasbourg
South Europe-Japan Joint Forum
South Europe - Japan Joint Forum on
Inorganic Chemistry and its Interfaces
organized by
with the support of
Scientific Coordinators
Munetaka Akita, Pierre Braunstein
Scientific Coordinators
France: Pierre Braunstein, UMR 7177 UdS-CNRS, Membre de l’Académie des Sciences
Japan: Munetaka Akita, Professor, Chemical Resources Laboratory, Tokyo Institute of Technology
Local Organizers
- Pierre Braunstein, UMR 7177 UdS-CNRS, Membre de l’Académie des Sciences
- Yoichi Nakatani, Professeur conventionné, UdS
- Hiroyuki Miyamoto, JSPS Strasbourg Office
- Pierre Rabu, IPCMS, UMR 7504
- Michael Chetcuti, ECPM, UMR 7509
Secretariat
- Atsuko Hisada, JSPS Strasbourg Office
- Rui Sakurai, JSPS Strasbourg Office
- Sandrine Garcin, UMR 7177 UdS-CNRS
South Europe – Japan Joint Forum « Inorganic Chemistry and Its Interfaces »
17-18 October 2014 Strasbourg, France
Objectives of the Forum
The recent international developments of inorganic chemistry can be explained not only by the fact that this chemistry applies to all the elements of the Periodic system but also because of its numerous interfaces with other disciplines and fields, themselves in very rapid growth.
Whether one considers synthetic molecular chemistry, bio-inorganic chemistry (models of enzymatic active sites), homogeneous and heterogeneous catalysis, the photocatalytic activation of small molecules, the synthesis of advanced molecules with high added-value via atom-economy processes, or supramolecular chemistry, the concepts and applications of inorganic chemistry are indispensable to deepen and expand our knowledge in these domains of considerable academic and industrial impact and relevance.
In particular, the catalytic activation by metal coordination using the most recently developed and efficient families of ligands, the bio-inspired catalytic production of dihydrogen, the electrochemical and photochemical activation processes related to solar cells, and inorganic materials endowed with unique magnetic or electric properties, will be at the focus of this symposium.
We wish to discuss the most recent advances made by highly recognised international groups in order to stimulate scientific exchanges and favour multidisciplinary collaborations by bringing in direct contact top scientists from Japan, France and south of Europe.
Since 2002, the University of Strasbourg has organised every year, in collaboration with the JSPS office in Strasbourg, a Franco-Japanese Forum dedicated to a different topic. The JSPS Strasbourg Office has been recently assigned the mission to develop exchanges with countries from southern Europe and with the French-speaking part of Switzerland. We wish to take this opportunity to organise a high-level Japan-Europe meeting in Strasbourg, a highly reputed site for the chemical sciences and located at the heart of Europe.
In this manner, we hope to promote new exchanges with Japan and between European countries and allow the French academic community (academic staffs and researchers) as well as students, in particular at the PhD level, to be exposed to an international research of excellence.
We wish you all a most fruitful forum, with numerous scientific exchanges and discussions with colleagues and hope that you will also enjoy the city of Strasbourg and its diverse facets.
Pierre Braunstein, Strasbourg Munetaka Akita, Tokyo
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South Europe-Japan Joint Forum on
Inorganic Chemistry and its Interfaces
October 17th, 2014 (Friday) 8 : 00 - Registration
Opening and Welcome Address
9 : 00 - 9 : 30 Alain BERETZ, President, University of Strasbourg Susumu HASEGAWA, Consul General of Japan in Strasbourg Chantal KHAN-MALEK, Deputy Director, Asia - Pacific, DERCI, CNRS Nicolas MATT, Vice - President, Communauté Urbaine de Strasbourg Michihisa KYOTO, Advisory Director, JSPS Tokyo
Session 1
Chairperson Yoichi NAKATANI, University of Strasbourg
9 : 30 - 10 : 15 Michael GRÄTZEL, Swiss Federal Institute of Technology « Light Energy Harvesting and Charge Carrier Collection in Mesoscopic Solar Energy Conversion Systems »
10 : 15 - 10 : 30 Coffee break
Session 2
Chairperson Andreas DANOPOULOS, USIAS Strasbourg
10 : 30 - 11 : 15 Munetaka AKITA, Tokyo Institute of Technology « Photoredox Catalysis : Organic Synthesis Promoted by Visible Light »
11 : 15 - 12 : 00 Vincent ARTERO, CEA, CNRS, Université Grenoble Alpes « Biomimetic, bioinspired and biosynthetic catalysts for water-splitting »
12 : 00 - 12 : 15 JSPS Presentation
12 : 15 - 12 : 30 Group photo
12 : 30 - Lunch (on invitation)
Session 3
Chairperson Michael CHETCUTI, ECPM Strasbourg
13 : 45 - 14 : 30 Kazunari DOMEN, University of Tokyo « Water Splitting on Heterogeneous Photocatalysts »
14 : 30 - 15 : 15 Avelino CORMA, University of Valencia « Solid catalysts for multistep reactions »
15 : 15 - 15 : 45 Coffee break
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Session 4
Chairperson Pierre RABU, IPCMS
15 : 45 - 16 : 30 Masako KATO, Hokkaido University « Luminescent Chromic Metal Complexes »
16 : 30 - 17 : 15 Luis ORO, University of Zaragoza « Mechanistic Studies on Rhodium-N-Heterocyclic Carbene Catalysts »
17 : 15 - 18 : 00 Tetsuro MURAHASHI, National Institutes of Natural Sciences « Chemistry of Dimensionally Extended Sandwich Complexes »
18 : 30 - Reception (on invitation)
October 18th, 2014 (Saturday) 8 : 30 - Registration
Session 5
Chairperson Vincent ROBERT, Institut de Chimie, Strasbourg
9 : 00 - 9 : 45 Armando POMBEIRO, University of Lisbon « From Electrocatalysis to Alkane Oxidation Catalysis with Inorganic Coordination Compounds »
9 : 45 - 10 : 30 Yoshiaki NISHIBAYASHI, University of Tokyo « Molybdenum-Catalyzed Reduction of Molecular Dinitrogen into Ammonia under Ambient Conditions »
10 : 30 - 11 : 00 Coffee break
Session 6
Chairperson Munakata AKITA, Tokyo Institute of Technology
11 : 00 - 11 : 45 Luisa de COLA, ISIS, University of Strasbourg « Dynamic and hybrid materials. Properties and applications »
11 : 45 - 12 : 30 Kazuyuki TATSUMI, Nagoya University « Organometallic Chemistry of Reductases – A Clue to Building a Future Sustainable Society –»
Closing remarks
12 : 30 - Hiroyuki MIYAMOTO, Director, JSPS Strasbourg Office Munekata AKITA, Tokyo Institute of Technology Pierre BRAUNSTEIN, University of Strasbourg
12 : 45 - Lunch (on invitation)
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Michael Grätzel
Laboratory of Photonics and Interfaces
Ecole polytechnique fédérale de Lausanne
CH-1015 Lausanne Switzerland
Professor at the Ecole polytechnique fédérale de Lausanne Professor Michael Grätzel directs there the Laboratory of
Photonics and Interfaces. He pioneered studies of mesoscopic materials and their use in energy conversion systems, in
particular photovoltaic cells and photo-electrochemical devices for solar generation of chemical fuels as well as lithium ions
batteries. He discovered a new type of solar cell based on sensitized nanocrystalline oxide films. His most recent awards
include the Leonardo Da Vinci Medal of the European Academy of Science, the Marcel Benoist Prize, the Albert Einstein
World Award of Science, the Paul Karrer Gold Medal, the Balzan Prize and the 2010 Millennium Technology Grand Prize. He
received a doctoral degree in Natural Science from the Technical University Berlin and was awarded honorary doctor’s
degrees from 10 European and Asian Universities. He is a member of the German Academy of Science (Leopoldina) the
Swiss Chemical Society and a Fellow of the European Academy of Science. He is Honorary Fellow the Royal Society of
Chemistry (UK) and the Max Planck Society. He is an elected honorary member of the Société Vaudoise de Sciences
Naturelles and the Bulgarian Academy of Science. Author of over 1000 publications and inventor of 50 patents he is with
some 130,000 citations and an h–index of 170 one of the 3 most highly cited chemists in the world.
Scientific Interests :
・Energy and eletron transfer reactions in mesoscopic systems
・Mesoscopic photovolataics
・Atrtificial photosynthesis
・Electricity storage in secondary batteries
Recent papers : 1) M. Grätzel, R. A. J. Janssen, D.B. Mitzi and E. H. Sargent, “Materials interface engineering for solution- processed
photovoltaics”, Nature 2012, 488, 304-312.
2) J.H Delcamp, A. Yella, T.W. Holcombe, and M.Grätzel, "The Molecular Engineering of Organic Sensitizers for Solar-Cell
Applications", Angew. Chem. Int. Ed., 2012, 52, 376-380
3) J. H. Heo, S. H. Im , J. H. Noh, T.N. Mandal, Ch.S. Lim J. A. Chang, Y.H.Lee, H.J Kim, A. Sarkar Md. K. Nazeeruddin, M.
Grätzel, and S. I. Seok, “Efficient inorganic–organic hybrid heterojunctionsolar cells containing perovskite compound and
polymeric hole conductors”, Nature Photonics 2013,.DOI: 10.1038/NPhoton2013.80
4) J.Brillet, J.-H. Yum, M. Cornuz, T. Hisatomi, R. Solarska, J.Augustynski, M. Grätzel and K.Sivula.“Highly efficient water
splitting by dual-absorber tandem cell“., Nature Photonics, 2012, 6, 824
5) J. Burschka, N. Pellet, S.-J. Moon, R.Humphry-Baker, P. Gao1, M K. Nazeeruddin1 and M. Grätzel, “ Sequential
deposition as a route to high-performance perovskite-sensitized solar cells” , Nature 2013, 499, 316-319
6) G.C. Xing, N. Mathews, S.Y. Sun, S.S. Lim, Y.M. Lam, M. Grätzel, S.Mhaisalkar, T.C. Sum "Long-Range Balanced
Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3", Science 2013, 342, 344-347.
7) S. C. Warren, K. Voïtchovsky, H. Dotan ,C. M. Leroy, M. Cornuz F. Stellacci, C., Hébert, A. Rothschild and M.Grätze
“Identifying champion nanostructures for solar water-splitting”, Nature Materials 2013, 12, 842–849
8) S. Mathew, A. Yella, P, Gao, R. Humphry-Baker, B.F.E. Curchod, N. Ashari-Astani I.Tavernelli, U. Rothlisberger, Md.K.
Nazeeruddin, M. Grätzel. „ Dye sensitized solar cell with 13% efficiency achieved through the molecular enginering of
prophyrin sensitizer“., Nature Chemistry DOI:10.1038/nchem.1861 (2014).
9) O. Malinkiewicz, A. Yella, Y.H.Lee, E.G.Minguez, M. Graetzel, M.K Nazeeruddin. H.J. Bolink “Perovskite solar cells
employing organic charge-transport layers”, Nature Photonics 2013, 8, 128-13.
10) A. Mei, X. Li, L.Liu, Z. Ku, T.Liu, Y. Rong, M. Xu, M.Hu, J. Chen, Yi. Yang, M.Grätzel, and H. Han “A hole-conductor free,
fully printable mesoscopic perovskite solar cell with high stability”, Science in press (2014).
4
Light Energy Harvesting and Charge Carrier Collection in
Mesoscopic Solar Energy Conversion Systems
Michael Grätzel
Station 6, LPI, ISIC EPFL Lausanne Switzerland
Phone: int+41-21-6933112, Fax: int+ 41-21-6936100
e-mail: [email protected] http://lpi.epf.ch
Solar cells using dyes or semiconducting pigment particles as light harvesters supported by mesoscopic oxide
films have emerged as credible contenders to conventional p-n junction photovoltaics 1 . Separating light
absorption from charge carrier transport, dye sensitized mesoscopic solar cells (DSSCs) were the first to use a
three-dimensional nanocrystalline junction for solar electricity production. Molecularly engineered donor-
acceptor porphyrine dyes reach currently a power conversion efficiency (PCE) of up to 13 percent 2,3 under
standard air mass 1.5 (AM1.5) reporting conditions (25°C, 1000 Watt/m2 solar intensity) Recently another
breakthrough was witnesses with the meteoric rise of metal halide perovskites as powerful light harvesters for
thin film photovoltaics 4. Solid state mesoscpic cells based on CH3NH3PbI3 pigments supported by a
nancorystalline TiO2 scaffold and organic or inorganic hole conductors have now reached a certified power
conversion efficiency of 17.9 % and further rapid improvements in performance appear to be feasible. Carrier
diffusion lengths extending over 100 mm have been measured 5 even from solution processed perovskite solar
cells (PVCs) and very stableef embodiments based on carbon current collectors have recently been realized.
1 Grätzel M. Nature 2001, 414, 338.
2 Yella,A.;. Lee, H.W. ;Tsao, H.N.; Yi, C.; .Kumar A.C.; Nazeeruddin; Md.K.; Diau E.-G.;, Yeh, C.-Y.; Zakeeruddin S. M.;
Grätzel ,M.; Science 2011, 629, 334.
3 Mathew, S.; Yella, A.; Gao, P, Humphry-Baker, R.; Curchod, B.F.E.; Ashari-Astani N.; Tavernelli,I..; Rothlisberger, U.;
Nazeeruddin, Md.K. ; Grätzel. M. Nature Chemistry 2014 DOI:10.1038/nchem.1861.
4 Burschka, J.; Pellet, N.; Moon, S.-J.; Humphry-Baker, R.; Gao, P.;. Nazeeruddin M K; Grätzel M. Nature 2013 499, 316.
5 Xing G.C., Mathews N., Sun S.Y., Lim S.S., Lam Y.M., Grätzel M., Mhaisalkar S., Sum T.C. Science 2013, 342, 344.
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Munetaka AKITA
Chemical Resources Laboratory
Tokyo Institute of Technology
Education: Kyoto University (Bachelor of Engineering ; 1979)
Graduate School of Kyoto University (Master of Engineering ; 1981)
Graduate School of Osaka University (Ph. D. ; 1984)
Scientific Interests : Organometallic Molecular Devices (Molecular Wire, Switch etc.)
Catalytic Reactions Promoted by Visible Light (Photoredox Catalysis)
Supramolecular Chemistry Based on Polyaromatic Systems
Recent papers : Review articles
Akita, M.; Koike, T., “Organometallic Chemistry of Polycarbon Species: From Clusters to Molecular
Devices”, Dalton Trans. 2008, 3523.
Inagaki, I.; Akita, M., “Visible-light Promoted Bimetallic Catalysis”, Coord. Chem. Rev. 2010, 254,
1220.
Akita, M. “Photochromic Organometallics, A Stimuli-responsive System: An Approach to Smart
Chemical Systems”, Organometallics 2011, 30, 43.
Koike, T.; Akita, M., “Visible-light-induced Photoredox Catalysis: An Easy Access to Green Radical
Chemistry”, Synlett 2013, 24, 2492.
Koike, T.; Akita, M., “Visible-Light-Induced Redox Reactions by Ruthenium Photoredox Catalyst”,
Top. Organomet. Chem.. 2014, in press (DOI: 10.1007/3418_2014_80).
Original papers relevant to photoredox catalysis
Koike, T.; Akita, M., “Photoinduced Oxyamination of Enamines and Aldehydes with TEMPO
Catalyzed by [Ru(bpy)3]2+”, Chem. Lett. 2009, 166.
Koike, T.; Yasu, Y.; Akita, M., “Three-component Oxytrifluoromethylation of Alkenes: Highly
Efficient and Regioselective Difunctionalization of C=C Bonds Mediated by Photoredox Catalysts”,
Angew. Chem. Int. Ed. 2012, 51, 9567.
Yasu, Y.; Koike, T.; Akita, M., “Intermolecular Aminotrifluoromethylation of Alkenes by Visible-
Light-Driven Photoredox Catalysis”, Org. Lett. 2013, 15, 2136.
Tomita, R.; Yasu, Y.; Koike, T.; Akita, M., “Integration of Trifluoromethylation and DMSO Oxidation
by Photoredox Catalysis: Facile Synthesis of α-Trifluoromethylated Ketones from
Aromatic Alkenes”, Angew. Chem. Int. Ed. 2014, 53, in press.
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Photoredox Catalysis: Organic Synthesis Promoted
by Visible Llight
Munetaka AKITA
Chemical Resources Laboratory, Tokyo Institute of Technology,
R1-27 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan
Phone & FAX: +81-45-924-5230
e-mail: [email protected] http://www.res.titech.ac.jp/~smart/smart_e.html
The sun provides huge and inexhaustible energy and has been regarded as a source of clean energy.
While much effort has been devoted to development of transformations of small inorganic molecules
(e.g. water splitting and CO2 reduction) promoted by visible light (sunlight), little attention has been
paid to application to organic transformations. During the last decade several research groups
including us have developed organic “photoredox catalysis” using the photo-harnessing [Ru(bipy)3]2+
and related Ir species (denoted as M).1
Visible light irradiation of M generates the excited species M* with two SOMOs, which can promote
oxidation and reduction of external substrates via SET processes in one catalytic cycle (reductive and
oxidative quenching cycles) with no need of addition of any sacrificial reagent (redox-neutral) to
generate two types of radical species, D+· and A-·, regarded as versatile synthetic intermediates.
On the basis of this principle, we developed a series of transformations of olefinic substrates
including oxyamination, C-C bond formation reactions, double functionalization, and
trifluoromethylation.
1 Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev., 2013, 113, 5322.
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Vincent ARTERO Laboratory of Chemistry and Biology of Metals
Université Grenoble Alpes - CNRS - CEA Grenoble
Education: Vincent Artero was born in 1973. He is a graduate of the Ecole Normale Supérieure
(Ulm) and of the University Pierre et Marie Curie (Paris 6). He received the Ph.D. degree in 2000 under
the supervision of Prof. A. Proust and Prof. P. Gouzerh. His doctoral work dealt with organometallic
derivatives of polyoxometalates. After a postdoctoral stay at the University of Aachen (RWTH) with Prof.
U. Kölle, he joined in 2001 the group of Prof. M. Fontecave in Grenoble where he obtained a position in
the Life Science Division of the CEA. Heʼs now group leader in the Laboratory of Chemistry and Biology
of Metals, cooperated by the Université Grenoble Alpes, the CNRS and the CEA in Grenoble.
Vincent Artero received the "Grand Prix Mergier-Bourdeix de l'Académie des Sciences" en 2011. In
2012 I was granted with a Starting Grant from the European Research Council (ERC). He's a member
of the Young academy of Europe (YAE). He currently acts as Chair of the Scientific Advisory Board of
the ARCANE Excellence Laboratory Network (LABEX) for bio-driven chemistry in Grenoble and as
vice-Chair of the COST action CM 1202 on Supramolecular Water Splitting.
Scientific Interests: Current research interests (see www.solhycat.com) are in the structural and functional modelisation
of hydrogenases, the design of artificial proteins and the design of novel nanomaterials for
hydrogen photo- and electro-production, hydrogen oxidation and CO2 reduction
Recent papers: “A Janus cobalt-based catalytic material for electro-splitting of water“ S. Cobo, J. Heidkamp, P.-A.
Jacques, J. Fize, V. Fourmond, L. Guetaz, B. Jousselme, V. Ivanova, H. Dau, S. Palacin, M. Fontecave
and V. Artero, Nature Materials, 2012, 11, 802-7.
“'Mesoporous -Fe2O3 Thin Films Synthesized via the Sol-gel Process for Light-driven Water Oxidation
“W. Hamd, S. Cobo, J. Fize, G.o Baldinozzi, W. Schwarz, M. Reymernier, A. Pereira, M. Fontecave, V.
Artero, C. Laberty-Robert and C. Sanchez, Phys. Chem. Chem. Phys., 2012, 14, 13224–13232.
“Molecular Engineering of a Cobalt-based Electrocatalytic Nano-Material for H2 Evolution under Fully
Aqueous Conditions“ E. Andreiadis, P.-A. Jacques, P. D. Tran, A. Leyris, M. Chavarot-Kerlidou, B.
Jousselme, M. Matheron, J. Pécaut, S. Palacin, M. Fontecave, V. Artero*, Nature Chemistry, 2013, 5,
48-53.
“Catalytic hydrogen oxidation: dawn of a new Iron Age“ T. R. Simmons, V. Artero*, Angew. Chem. Int.
Ed., 2013, 52, 6143-45.
“Biomimetic assembly and activation of [FeFe]-hydrogenases“ G. Berggren, A. Adamska, C. Lambertz,
T. R. Simmons, J. Esselborn, M. Atta, S. Gambarelli, JM Mouesca, E. Reijerse, W. Lubitz, T. Happe, V.
Artero, M. Fontecave*; Nature, 2013, 499, 66-69.
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Biomimetic, bioinspired and biosynthetic catalysts for
water-splitting
Vincent ARTERO
Laboratory of Chemistry and Biology of Metals (Université Grenoble Alpes – CNRS – CEA Grenoble)
17 rue des Martyrs; 38054 Grenoble Cedex 9
Phone:+33681265403 Fax: +33438789124
e-mail: [email protected] http://www.solhycat.com/
Hydrogen production, through the reduction of water in electrolysers, is currently one of the most
convenient ways to store energy durably. However the viability of a hydrogen economy depends on the
design of new efficient and robust electrocatalytic materials based on earth-abundant elements.1A
competitive alternative to platinum could be found in living micro-organisms metabolizing hydrogen
thanks to hydrogenases. Catalysis in hydrogenases only requires base-metal centers (nickel and iron)
and we will show how their active sites can be used as an inspiration to design new synthetic catalysts 2
and we will present very recent results related to the use of these structural mimics for the development
of biotechnological processes.3 We will then present the bio-inspired approach that we develop for a
decade in the lab. We found that cobalt diimine-dioxime complexes4 are efficient and stable electro-
catalysts for hydrogen evolution form acidic non-aqueous solutions with slightly lower overvoltages and
much larger stabilities towards hydrolysis as compared to previously reported cobaloxime catalysts. 1
We will report on different approaches for the covalent functionalization of electrode materials with such
catalysts and their activity under fully aqueous conditions.5
1 Artero, V.; Chavarot-Kerlidou, M.; Fontecave, M. Angew. Chern. Int. Ed. 2011,50, 7238
2 Canaguier, S.; Field, M.; Oudart, Y.; Pecaut, J.; Fontecave, M.; Artero, V. Chern. Cornrnun. 2010,46,5876
3 Berggren, G.; Adamska, A.; Lambertz, C.; Simmons, T. R.; Esselborn, J.; Atta, M.; Gambarelli, S.; Mouesca, J.
M.; Reijerse, E.; Lubitz, W.; Happe, T.; Artero, V.; Fontecave, M. Nature 2013, 499, 66; Esselborn, J.; Lambertz,
C.; Adamska-Venkatesh, A.; Simmons, T.; Berggren, G.; Noth, J.; Siebel, J.; Hemschemeier, A.; Artero, V.;
Reijerse, E.; Fontecave, M.; Lubitz, W.; Happe, T. Nat Chern BioI 2013, 9, 607.
4 Jacques, P.-A.; Artero, V.; Pecaut, J.; Fontecave, M. Proc. Nat!. Acad. Sci. U.S.A. 2009, 106,20627
5 Andreiadis, E. S.; Jacques, P.-A.; Tran, P. D.; Leyris, A.; Chavarot-Kerlidou, M.; Jousselme, B.; Matheron, M.;
Pecaut, J.; Palacin, S.; Fontecave, M.; Artero, V. Nat. Chern. 2013,5,48
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Kazunari DOMEN School of Engineering, the University of Tokyo
Professor
Education: B.S.c. (1976), M.S.c. (1979), and Ph.D. (1982) honors in chemistry from
the University of Tokyo.
Scientific Interests : Domen has been working on overall water splitting reaction on heterogeneous photocatalysts to
generate clean and recyclable hydrogen. His research interests now include heterogeneous catalysis
and materials chemistry, with particular focus on surface chemical reaction dynamics, photocatalysis,
solid acid catalysis, and mesoporous materials.
Recent papers : Maeda, K.; Domen, K. J. Phys. Chem. Lett. 2010, 1, 2655.
Hisatomi, T.; Kubota, J.; Domen, K.; Chem. Soc. Rev. DOI:10.1039/C3CS60378D.
Li, Y.; Zhang, L.; Torres-Pardo, A.; Gonzalez-Calbet, J. M.; Ma, Y.; Oleynikov, P.; Terasaki, O.;
Asahina, S.; Shima, M.; Cha, D.; Zhao, L.; Takanabe, K.; Kubota, J.; Domen, K. Nat. Comm. 2013,
4, 2566.
Minegishi, T.; Nishimura, N.; Kubota, J.; Domen, K. Chem. Sci. 2013, 4, 1120.
Moriya, M.; Minegishi, T.; Kumagai, H.; Katayama, M.; Kubota, J.; Domen, K. J. Am. Chem. Soc.
2013, 135, 3733
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Water Splitting on Heterogeneous Photocatalysts
Kazunari DOMEN
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656
Phone:+81 3 5841 1148, Fax: int+81 3 5841 8838
e-mail: [email protected]
Solar hydrogen production from water using semiconductor photocatalysts and photoeletrodes has
attracted much attention as a technology for artificial photosynthesis to solve energy and
environmental problems.1,2 When a semiconductor absorbs a photon that has energy larger than the
band gap of the semiconductor, an electron in the valence band is excited to the conduction band, and
a positive hole is left behind. These photoexcited carriers can drive redox reactions depending on the
potential of the band edges. A semiconductor can split water into hydrogen and oxygen when the band
gap straddles both hydrogen evolution and oxygen evolution reactions (Fig. 1a). Additionally, two
different photocatalysts can be connected in series to generate hydrogen and oxygen on the
respective photocatalysts. This process based on two-step excitation is often called Z-scheme. A
semiconductor photocatalyst can also be applied as a
photoelectrode for water splitting when it is immobilized or
directly prepared on a conductive substrate (Fig. 1b). In
either case, it is necessary to improve the properties of
narrow band gap semiconductors to harvest the sunlight
effectively. In addition, modification of the semiconductor
photocatalyst surface is generally necessary to enhance
charge separation and surface redox reactions and thereby
to improve the quantum efficiency at the respective
wavelengths.
The author has developed new photocatalytic materials
with suitable band gap energies and positions. It has been
proven that some (oxy)nitrides and (oxy)chalcogenides work
as promising photocatalysts and photoelectrodes for water
splitting under visible light irradiation.3 Recent progress on
non-oxide photocatalysts for water splitting will be
presented in the talk.
1 Maeda, K.; Domen, K. J. Phys. Chem. Lett. 2010, 1, 2655.
2 Hisatomi, T.; Kubota, J.; Domen, K.; Chem. Soc. Rev. DOI:10.1039/C3CS60378D.
3 Maeda, K.; Domen, K. J. Phys. Chem. C 2007, 111, 7851.
H+ / H2
O2 / H2O
Band gap
2 H+
H2
+1.0
+2.0
+3.0
0
hn
O2 + 4 H+
2 H2OVB
CB
h+
e－
(-)
(+)Po
ten
tia
l/
V v
s.
NH
E(p
H 0
)
(a)
Photocatalyst
e-
h+
e-
1.23 Vhn
Photoanode Counter
electrode
e-
(b)
CB
VB
+1.0
+2.0
+3.0
0
(-)
(+)Po
ten
tia
l/
V v
s.
NH
E(p
H 0
)
H+/H2
O2/H2O
Figure 1. Energy diagrams of (a)
photocatalytic and (b) photoelectrochemical
water splitting based on one-step
excitation. CB: conduction band, VB:
valence band.
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Avelino Corma Canos Instituto de Tecnología Química (UPY-CSIC)
Education: Postdoct, Queen´s University, Canada (1977- 1979)
Phd in Chemistry, 1976, Universidad Complutense de Madrid
(Advisor: Professor Antonio Cortes)
Summa Cum Laude
Degree in Chemistry, 1974; Universidad de Valencia
Scientific Interests : Molecular Sieves synthesis and catalysis, metal nanoparticles and clusters synthesis and catalysis.
Multifunctional catalysis
Molecular sieves, Multifunctional catalysts metal nanoparticles catalysts, Multifunctional catalyst.
Recent papers : A. CORMA, P. CONCEPCION, M. BORONAT, M. J. SABATER, J. NAVAS, M. YACAMAN, E. LARIOS,
A. POSADAS, A. M. LOPEZ-QUINTELA, D. BUCETA
“Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity”
Nature Chemistry 5(9), 775-781 (2013)
J. JIANG, J.L. JORDA, J. YU, L.A. BAUMES, E. MUGNAIOLI, M.J. DIAZ-CABANAS, U. KOLB, A.
CORMA
“Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43 “
SCIENCE (Washington, DC, USA) 333(6046), 1131-1134, (2011)
R. SIMANCAS, D. DARI, N. VELAMAZAN, M.T. NAVARRO, A. CANTIN, J.L. JORDA, G. SASTRE,
A. CORMA, F. REY
“Modular Organic Structure-Directing Agents for the Synthesis of Zeolites “
SCIENCE (Washington, DC, USA) 330(6008), 1219-1222. (2010)
J. SUN, C, BONNEAU, A. CANTIN, A. CORMA, M. DIAZ-CABANAS, M. MOLINER, D. ZHANG, M. LI,
X. ZOU
“The ITQ-37 mesoporous chiral zeolite”
Nature (London, UK). 458(7242), 1154-1157 (2009)
A. CORMA
“Materials chemistry: catalysts made thinner”
Nature 461, 182-3 (2009)
A. GIRRANE, A. CORMA, H. GARCÍA
“Gold catalyzed synthesis of aromatic azo compounds from anilines and nitroaromatics”
SCIENCE 322(5908), 1661-166 (2008).
12
Solid catalysts for multistep reactions
Avelino Corma
Instituto de Tecnología Química, UPV-CSIC
Universitat Politécnica de Valencia
Avda. de los Naranjos s/n
46022-Valencia –SPAIN
In an approach to design selective solid catalysts we start from the knowledge, at the molecular level,
of the reaction to be catalyzed. Then hypothesis are made on the nature of the active sites required. At
this point we are ready to synthesize solid materials, in where the required active sites are introduced
as well defined entities. On top of that the adsorption properties of the solid are taylored to optimize
the interactions between reactants, catalyst and products. Following this methodology will present
solid catalysts in where the active sites correspond to well defined transition metal complexes and
organocatalysts that are either grafted or structurally builded into solids. In this case, the role of the
solid can go beyond a simple support, since it is designed to intervene in the reaction either by
stabilizing transition states or by introducing additional active sites.
Well defined single or multiple active sites can also be introduced into crystalline nanoporous materials
with controlled adsorption properties, and this allows to perform new acid and redox, one step or
multistep reactions. Finally will show that by depositing metal nanoparticles or metal clusters (Au, Pd,
Pt) on proactive supports (CeO2, Fe2O3, MgO, hydrotalcites, etc.) we can open new catalytic reaction
routes for C-C bond formation, oxidations and reductions. These catalytic system allow the design of
multifunctional solid catalysts that are able to carry out multistep process through cascade type
reactions that were not possible before.
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Masako KATO Department of Chemistry, Faculty of Science,
Hokkaido University
Education: Dr. Sc., Nagoya University, Aichi, Japan in 1986
Staff Scientist at Institute for Molecular Science in 1981
Staff Scientist at Department of Chemistry, Kyoto University in 1985
Assistant Prof. in 1989 and Associate Prof. in 1997 at Nara Women’s University, Nara, Japan
Prof. at Hokkaido University, Hokkaido, Japan in 2006
Scientific Interests: Construction of new chromic materials based on luminescent metal complexes
Fabrication of novel 3d-metal complexes with intense luminescence
Development of catalytic systems using photofunctional metal complexes
Recent papers: H. Ohara, A. Kobayashi, and M. Kato, "Simple Manual Grinding Synthesis of Highly Luminescent
Mononuclear Cu(I)-Iodide Complexes", Chem.Lett. 2014, in press.
Kobayashi, D. Yamamoto, H. Horiki, K. Sawaguchi, T. Matsumoto, K. Nakajima, H.-C. Chang and
M. Kato, "Photoinduced Dimerization Reaction Coupled with Oxygenation of a
Platinum(II)−Hydrazone Complex", Inorg. Chem. 2014, 53, 2573−2581.
T. Ohba, A. Kobayashi, H.-C. Chang, T. Kouyama, T. Kato, and M. Kato, "Hysteretic vapour
response of a heterodinuclear platinum(II)-copper(II) complex derived from the dimer-of-dimer
motif and the guest-absorbing site", Dalton. Trans. 2014, 43, 7514-7521.But please try to identify
recent, key papers in your areas of interest
Kobayashi, K. Komatsu, H. Ohara, W. Kamada, Y. Chishina, K. Tsuge H.-C. Chang, and M. Kato,
"Photo- and Vapor-Controlled Luminescence of Rhombic Dicopper(I) Complexes Containing
Dimethyl Sulfoxide", Inorg. Chem. 2013, 52, 13188-13198.
T. Matsumoto, H.-C. Chang, M. Wakizaka, S. Ueno, A. Kobayashi, A. Nakayama, T. Taketsugu
and M. Kato, "Non precious-metal-assisted Photochemical Hydrogen Production from ortho-
Phenylenediamine", J. Am. Chem. Soc. 2013, 135, 8646-8654.
T. Ohba, A. Kobayashi, H.-C. Chang and M. Kato, "Vapour and mechanically induced chromic
behaviour of platinum complexes with a dimer-of-dimer motif and the effects of hetero metal ions",
Dalton. Trans., 2013, 42, 5490-5499.
Kobayashi, Y. Fukuzawa, H.-C. Chang, and M. Kato, "Vapor-Controlled Linkage Isomerization of
a Vapochromic Bis(thiocyanato)platinum(II) Complex: New External Stimuli to Control
Isomerization Behavior", Inorg. Chem. 2012, 51, 7508-7519.
14
Luminescent Chromic Metal Complexes
Masako KATO
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, 060-0810, Japan
Phone: +81-11706-3817, Fax: +81-11706-3447
e-mail: [email protected] http://wwwchem.hokudai.ac.jp/~cc/
Luminescent metal complexes have remarkably developed recently as phosphorescent materials for
organic light-emitting devices, photosensitizers for photocatalytic systems, and chromic materials for
volatile organic compound (VOC) sensors. Platinum(II) complexes have been extensively studied from
the viewpoint of their characteristic luminescence by assembling.1 Copper(I) complexes attract much
attention as inexpensive and abundant non-noble metal luminescent materials. This presentation
focuses on the latest interesting topics concerning chromic metal complexes found in our group.
1. Vapour and mechanically induced chromic behaviour of homo- and hetero-
dinuclear platinum complexes. 2 The hexafluorophosphate salt of a dinuclear
platinum(II) complex, [Pt2(μ-pyt)2(bpy)2]2+ (pyt = pyridine-2-thiolate, bpy = 2,2′-
bipyridine) exhibits a remarkable luminescence change on the absorption/desorption
of vapor molecules such as acetonitrile.3 The introduction of heterometal ions into
the dinuclear unit enabled to control of the chromic region. We clarified that the
vapochromic behavior arises from the formation and breaking of the intermolecular
Pt⋯Pt interaction of the dimer-of-dimer motif. In addition, these complexes were
found to exhibit mechanochromic behaviour based on the crystal-to-amorphous
transformation.
2. Hightly luminescent copper(I)-halide compelxes: mononuclear complexes formed by simple
grinding and dinuclear complexes exhibitting photo- and vapor-controlled luminescence.4,5 We found
that mononuclear copper(I) complexes, [CuI(L)(PPh3)2] (N-heteroaromatic ligands) were synthesized
easily and efficiently by simple manual grinding of the materials. These complexes exhibit strong
emission with the high quantum yield of 0.63-0.99 and the emission color depends on π-conjugation of
L ligands. On the other hand, the iodide-bridged dinuclear copper(I) complex, [Cu2(μ-
I)2(dmso)2(PPh3)2] (dmso = dimethyl sulfoxide) exhibits the photo-induced color change in the
luminescence from blue to green on irradiation of the light (λ = 350 nm) and the recovery in the dmso
atmosphere. This unique chromic behavior occurs on the basis of the change in the coordination mode
and the absorption/desorption of dmso molecules.
1 Kato, M. Bull. Chem. Soc. Jpn. 2007, 8, 287.
2 Ohba, T.; Kobayashi, A.; Chang, H.-C.; Kato, M. Dalton Trans. 2013, 42, 7514.
3 Kato, M.; Omura, A.; Toshikawa, A.; Kishi, S.; Sugimoto, Y. Angew. Chem., Int. Ed., 2002, 41, 3183.
4 Ohara, H.; Kobayashi, A; and Kato, M. Chem.Lett. 2014, in press.
5 Kobayashi, A; Komatsu, K.; Ohara, H.; Kamada, W.; Chishina, Y.; Tsuge, K.; Chang, H.-C.; M. Kato, M. Inorg.
Chem. 2013, 52, 13188.
dimer-of-dimer
strcuture
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Luis ORO Department of Inorganic Chemistry University of Zaragoza, Spain http://sorores.unizar.es/personales/LAO/oro.html Education: Luis A. Oro obtained his Ph. D. from the University of Zaragoza in 1970. He was a postdoctoral
fellow at Cambridge University under the supervision of Professor the Lord Lewis from 1972 to 1973. It was
during this time that he became interested in organometallic chemistry. He has served on the faculties of the
Universities of Zaragoza, Madrid Complutense, and Santander. He became full professor of Inorganic Chemistry
in Zaragoza in 1982. His main research interests are in the organometallic chemistry and homogeneous catalysis
area. He has coauthored well over 500 scientific papers and several reviews on synthesis, reaction mechanisms
and homogeneous catalysis. He is co-author or co-editor of several books. He is co-chairman of the Editorial
Board of ChemCatChem and Series Editor of Topics in Organometallic Chemistry. He is also member of the
Editorial Advisory Board of several international journals.
He is member of the German National Academy of Sciences Leopoldina, foreign member of the “Académie de
Sciences” (France), and member of the Academia Europaea (London), the Hungarian Academy of Sciences and
the European Academy of Sciences. He has received several distinctions and prizes, such as the Solvay Prize,
Humboldt Research Award, King James I Research Prize, Aragón Prize, Sacconi Medal, Honoris Causa
Doctorate from the University of Rennes, Gold Medal of the Spanish Royal Society of Chemistry and National
Research Prize for Chemistry. He has been President of the European Association for Chemistry and Molecular
Sciences (EuCheMS) (2008-11).
Scientific Interests : Synthesis, structure and reactivity of organometallic complexes.
Homogeneous catalysis by complexes of rhodium and iridium in reactions of hydrogenation,
hydrogen transfer, hydrosilylation, hydrothiolation, hydroamination, ……...
C-H, NH3 and CO2 activation.
Recent papers : Homogeneous catalytic reduction of CO2 with hydrosilanes., Catal. Sci. Technol., 4, 1609-1619 (2014).
P-H activation of secondary phospanes on a parent amido diiridium complex, Dalton Trans., 43, 1609-1619
(2014).
An alternative mechanistic paradigm for the b-(Z)-hydrosilylation of terminal alkynes: the role of acetone as
silane shuttle., Chem. Eur. J., 19, 17559-17566 (2013).
Hydroxide-rhodium–N-heterocyclic carbene complexes as efficient catalysts for alkyne hydrothiolation, ACS
Catalysis, 3, 2910-2919 (2013).
CO2 activation and catalysis driven by iridium complexes, ChemCatChem, 5, 3481-3494 (2013).
Terminal and bridging parent amido 1,5-cyclooctadiene complexes of rhodium and iridium. , Chem. Eur. J., 19,
5665-5676 (2013).
The emergence of transition metal-mediated hydrothiolation of unsaturated carbon-carbon bonds: a
mechanistic outlook, Angew. Chem. Int. Ed., 52, 211-222 (2013).
Effective fixation of CO2 by iridium-catalysed hydrosilylation, Angew. Chem. Int. Ed., 51, 12824-12827 (2012).
Ligand-controlled regioselectivity in the hydrothiolation of alkynes by rhodium N-Heterocyclic carbene
catalysts., J. Am. Chem. Soc., 134, 8171-8183 (2012).
The dehydrogenation of alcohols through a concerted bimetallic mechanism Involving an amido-bridged
diiridium complex., Angew. Chem. Int. Ed., 51, 8259-8263 (2012).
Direct access to parent amido complexes of rhodium and Iiidium through N-H activation of ammonia., Angew.
Chem. Int. Ed., 50, 11735-11738 (2011).
Mild and selective H/D exchange at the -position of aromatic a-olefins by N-heterocyclic carbene-hydride-
rhodium catalysts., Angew. Chem. Int. Ed., 50, 3938-3942 (2011).
16
Mechanistic Studies on Rhodium-N-Heterocyclic Carbene
Catalysts
Luis A. ORO
Department of Inorganic Chemistry, University of Zaragoza, Pedro Cerbuna 12, 50009-Zaragoza,
Phone: int+ 34 976 76 11 43
e-mail: [email protected] http://sorores.unizar.es/personales/LAO/oro.html/
The catalytic activity of a set of rhodium complexes with N-heterocyclic carbene (NHC) ligands1 in
two specific homogeneous reactions, alkyne hydrothiolation and vinyl selective H/D exchange, has
been studied. The high steric hindrance and powerful electron-donor capacity of the bulky NHC´s used,
along with ancillary N-donor ligands, seems to be determinant to get selective transformations and to
facilitate valuable information about the mechanism of the mentioned reactions.
Rhodium(I) compounds of formula [Rh(μ-X)(IPr)(η2-olefin)]2 (X = Cl, OH), RhCl(IPr)(py)(η2-olefin) and
Rh(oq)(IPr)(η2-olefin) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene, py = pyridine, oq =
quinolinolate) are very active catalysts for alkyne hydrothiolation under mild conditions, presenting
high selectivity towards α-vinyl sulfides. Several intermediates relevant for the catalyt ic process have
been detected. All the studied rhodium carbene catalysts have in common a mechanism that proceed
via oxidative addition of the S-H bond to rhodium(I) intermediates and successive alkyne insertion into
the Rh-S bond followed by reductive elimination steps.
A series of rhodium(III)-NHC complexes containing H-Rh-NHC and C2H5-Rh-NHC frameworks and
quinolinato or acetonitrile ligands are active and selective catalysts for the H/D exchange of aromatic
α- olefins, using CD3OD as deuterium source. Most of these complexes resulted to be selective in the
vinylic-H/D exchange of styrene without the concomitant deuteration of the aromatic region, being able
to deuterate the vinylic β-positions with very high selectivity. The proposed mechanism implies an
initial H/D exchange, a 1,2 or 2,1 insertion of the coordinated olefin on the Rh-D bond, to give linear or
branched alkyl products, followed by rotation and β-elimination (Figure). Interestingly, the steric
constraints exerted by the bulky IPr NHC ligand control the rotation of the alkyl intermediate, which in
turn determines the selectivity towards H/D exchange at the β-position of aromatic α-olefins.
1 Castarlenas, R.; Oro, L.A. et al.; ACS Catalysis 2013, 3, 2910; Angew. Chem. Int. Ed., 2013, 52, 211; J. Am.
Chem. Soc., 2012,134, 8171; Angew. Chem. Int. Ed., 2011, 50, 3938.
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Tetsuro MURAHASHI Professor, Institute for Molecular Science,
National Institutes of Natural Sciences
Education and Research Activities: 1995: B. S. Osaka University, Japan
1999: Ph. D. Osaka University, Japan
Supervisor: Prof. Hideo Kurosawa (Mechanistic Organometallic Chemistry)
1999-2007: Assistant Professor, Department of Applied Chemistry, Osaka University
2003-2005: Japan Society for the Promotion of Science (JSPS) Research Abroad (MIT, USA)
Supervisor: Prof. Christopher C. Cummins (Dinitrogen Activation Chemistry)
2005-2009: PRESTO researcher, Japan Science and Technology Agency (JST)
2007-2012: Associate Professor, Department of Applied Chemistry, Osaka University
2010-2014: PRESTO researcher, Japan Science and Technology Agency (JST)
2012- : Professor, Institute for Molecular Science (IMS)
2012- : Professor, Department of Structural Molecular Science, The Graduate University for Advanced Studies
2007: Chemical Society of Japan Award for Young Chemists
2008: Japan Society of Coordination Chemistry Award for Young Chemists
2008: The Young Scientist Prize, The Commendation for Science and Technology by the Minister of Education,
Culture, Sports, Science, and Technology, Japan
2010: Royal Society of Chemistry, Dalton Asian Lectureship Award
Scientific Interests: Synthetic Inorganic and Organometallic Chemistry, Mechanistic Study of Important, Organometallic Reactions
and Catalysis
Main keywords: Inorganic Synthesis; Transition Metal Chemistry; Metal Clusters, Catalysis
Recent papers : (1) “Bis-cyclooctatetraene Tripalladium Sandwich Complexes”, T. Murahashi, S. Kimura, K. Takase, T. Uemura, S. Ogoshi, K.
Yamamoto, Chem. Commun. 2014, 50, 820-822.
(2) “Trinuclear Palladium Addition to Unsaturated Carbocycles”, T. Murahashi, K. Takase, K. Usui, S. Kimura, M. Fujimoto, T.
Uemura, S. Ogoshi, K. Yamamoto, Dalton Trans. 2013, 42, 10626-10632.
(3) “Redox-induced Reversible Metal Assembly through Translocation and Reversible Ligand Coupling in Tetranuclear Metal
Sandwich Framework”, T. Murahashi, K. Shirato, A. Fukushima, K. Takase, T. Suenobu, S. Fukuzumi, S. Ogoshi, H.
Kurosawa, Nature Chem. 2012, 4, 52-58.
(4) “Oxidative Dinuclear Addition of a PdI-PdI Moiety to Arenes: Generation of μ-ƞ3-ƞ3-Arene PdII, 2 Species”, T. Murahashi, K.
Takase, M. Oka, S. Ogoshi, J. Am. Chem. Soc. 2011, 133, 14908-14911.
(5) “Metallocenoids of Platinum: Syntheses and Structures of Triangular Triplatinum Sandwich Complexes of Cycloheptatrienyl”,
T. Murahashi, K. Usui, R. Inoue, S. Ogoshi, H. Kurosawa, Chem. Sci. 2011, 2, 117-122.
(6) “Square Tetrapalladium Sheet Sandwich Complexes: Cyclononatetraenyl as a Versatile Face-Capping Ligands”, T.
Murahashi, R. Inoue, K. Usui, S. Ogoshi, J. Am. Chem. Soc. 2009, 131, 9888-9889.
(7) “Reductive Coupling of Metal Triangles in Sandwich Complexes”, T. Murahashi, Y. Hashimoto, K. Chiyoda, M. Fujimoto, T.
Uemura, R. Inoue, S. Ogoshi, H. Kurosawa, J. Am. Chem. Soc. 2008, 130, 8586-8587.
(8) “Discrete Triangular Tripalladium Sandwich Complexes of Arenes”, T. Murahashi, M. Fujimoto, Y. Kawabata, R. Inoue, S.
Ogoshi, H. Kurosawa, Angew. Chem. Int. Ed. 2007, 46, 5440-5443.
(9)"Discrete Sandwich Compounds of Monolayer Palladium Sheets", T. Murahashi, M. Fujimoto, M. Oka, Y. Hashimoto, T.
Uemura, Y. Tatsumi, Y. Nakao, A. Ikeda, S. Sakaki, H. Kurosawa, Science, 2006, 313, 1104-1107.
18
Chemistry of Dimensionally Extended Sandwich Complexes
Tetsuro MURAHASHI
Institute for Molecular Science, National Institutes of Natural Sciences, Myodaiji, Okazaki, Aichi
4448787, JAPAN Phone: int+81-564-59-5580,Fax: int+81-564-59-5582 e-mail:[email protected];
http://groups.ims.ac.jp/organization/murahashi_g/english.html
The sandwich structure is one of the fundamental structural motifs for transition metal complexes.
Most of sandwich complexes contain a mononuclear metal moiety between parallel cyclic unsaturated
hydrocarbon ligands. On the other hand, it had been difficult to synthesize stable sandwich complexes
in which a metal assembly is sandwiched
between two parallel unsaturated
hydrocarbons. Our group discovered that
multinuclear sandwich complexes exist as
isolable molecules (Figure 1).1,2
It has been
shown that various pπ-conjugated
unsaturated hydrocarbons, such as linear π-
conjugated polyenes, monocyclic aromatic
hydrocarbons, and polycyclic arenes form
multinuclear sandwich complexes having
different size and shape of metal chains or
metal sheets. Furthermore, we also revealed
some unique chemical properties of
multinuclear sandwich complexes stemming
from the (π--conjugated unsaturated
hydrocarbon)-(multinuclear metal) hybrid
structures.
In this presentation, recent development in
the chemistry of multinuclear sandwich
complexes will be overviewed; e.g., tailor-made construction of metal assembly in organometallic
sandwich framework, 3 , 4 and elucidation of unique dynamic structural changes induced by redox
reactions or photo-irradiation.5
1 T. Murahashi, E. Mochizuki, Y. Kai, H. Kurosawa, J. Am. Chem. Soc. 1999, 121, 10660.
2 T. Murahashi, M. Fujimoto, M. Oka, Y. Hashimoto, T. Uemura, Y. Tatsumi, Y. Nakao, A. Ikeda, S. Sakaki, H.
Kurosawa, Science, 2006, 313, 1104.
3 T. Murahashi, R. Inoue, K. Usui, S. Ogoshi, J. Am. Chem. Soc. 2009, 131, 9888.
4 T. Murahashi, K. Takase, M. Oka, S. Ogoshi, J. Am. Chem. Soc. 2011, 133, 14908.
5 T. Murahashi, K. Shirato, A. Fukushima, K. Takase, T. Suenobu, S. Fukuzumi, S. Ogoshi, H. Kurosawa, Nature
Chem. 2012, 4, 52.
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Armando J. L. POMBEIRO Centro de Química Estrutural, Instituto Superior Tecnico, Universidade de Lisboa Education and Scientific Interests: Armando J. L. Pombeiro is Full Professor at the Instituto Superior Técnico, Full Member of the
Academy of Sciences of Lisbon (enrolled in various directive and representative positions), President of
the Portuguese Electrochemical Society, and Director of the PhD program on Catalysis and Sustainability (CATSUS). He
teaches the Homogeneous Catalysis course at the Multinational Master in Molecular Chemistry at the École Polytechnique,
Paris, and is Invited Chair Professor at the National Taiwan University of Science and Technology.
His research group investigates the activation of small molecules with industrial, environmental or biological significance,
including metal-mediated synthesis and catalysis (e.g., functionalization of alkanes under mild conditions), crystal engineering
of coordination compounds, design and self-assembly of polynuclear and supramolecular structures, molecular
electrochemistry and theoretical studies.
He was chairman or member of organizing/scientific committees of 40 international conferences or schools (e.g., the XXV
Intern. Conference on Organometallic Chemistry). He authored or edited 4 books, (co-)authored over 600 research
publications, 33 patents, and presented 95 invited lectures at intern. conferences. His work has received ca. 12,000 citations,
h-index over 50 (Web of Science). Among his honors, he has been awarded the Madinabeitia-Lourenço Prize from the
Spanish Royal Chemical Society, and the Ferreira da Silva Prize from the Portuguese Chemical Society.
Keywords: transition metal complexes, catalysis, metal-mediated synthesis, molecular electrochemistry, theoretical studies,
activation of small molecules, alkane functionalization, alcohol oxidation, C-C couplings, cycloadditions, nitriles, isocyanides,
self-assembled metal assemblies, coordination polymers, MOFs.
http://cqe.ist.utl.pt/personal_pages/pages/armando_pombeiro.php
Recent papers representative of the various research areas: • A.J.L. Pombeiro (Ed.), “Advances in Organomet. Chem. and Catalysis” (The Silver/Gold Jubilee ICOMC Celebratory Book), J. Wiley, 2014,
Chs. 2, 3, 18, 19, 22 and 50.
• J.A.L. da Silva et al., “Amavadin, a Vanadium Natural Complex…”, Coord. Chem. Rev., 2013, 257, 2388.
• M. Sutradhar et al, “… vanadium(IV/V) complexes with azine fragment ligands”, Coord. Chem. Rev., 2014, 265, 89-124.
• K.T. Mahmudov et al, “…arylhydrazones of methylene active compounds”, Coord. Chem. Rev., 2013, 257, 1244.
• V.Yu. Kukushkin et al, “Additions to Metal-Activated Organonitriles”, Chem. Rev., 2002, 102, 1771.
• M.V. Kirillova et al, ”Alkanes to Carboxylic Acids in Aqueous Medium…”, Chem. Commun., 2009, 2353.
• T.F.S. Silva et al, “Scorpionate and Pyrazole Dioxovanadium Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes”, Adv. Synth.
Cat., 2010, 352, 171.
• D.S. Nesterov et al, “Heterometallic CoIII4FeIII2 Schiff Base Complex:kane Oxidation Catalytic Activity”, Inorg.Chem., 2012, 51, 9110.
• M. Kuznetsov et al, “Radical Formation in [MeReO3] Catalyzed Aqueous Peroxidative Oxidation of Alkanes…”, Inorg. Chem., 2009, 48, 307.
• M.V. Kirillova et al, ”Mechanism of H2O2 Oxidations Catalyzed by Vanadate or Vanadatrane...”, J. Cat., 2009, 267, 140.
• P.J. Figiel et al ,“ Solvent-free Microwave-assisted Peroxidative Oxidation of Alcohols to Ketones Catalyzed by Copper(II) Complexes…”,
Chem. Commun., 2010, 46, 2766.
• R.R. Fernandes et al, “Pd(II) Complexes as Highly Efficient Catalysts for Suzuki-Miyaura Reactions in Supercritical CO2…”, Adv. Synth.
Cat., 2011, 353, 1153.
• M.N. Kopylovich et al, “H-Bond Assisted Activation of a Dinitrile towards Nucleophilic Attack”, Chem. Commun., 2011, 47, 7248.
• X. Shang et al, "Electrochemical and Theoretical Studies and Antitumor Activities of Organotin(IV) Complexes …", Inorg. Chem., 2011, 50,
8158.
• M.V. Kirillova et al, “Direct Conversion of Methane into Acetic Acid Catalyzed by Amavadine …”, J. Am. Chem. Soc., 2007, 129, 10531.
• A.M. Kirillov et al, “Multinuclear Cu Complexes as Catalysts for Peroxidative Oxidation of Alkanes ...”, Angew. Chem., Int. Ed., 2005, 44,
4345.
20
From Electrocatalysis to Alkane Oxidation Catalysis with
Inorganic Coordination Compounds
Armando J. L. POMBEIRO Centro de Química Estrutural, Instituto Superior Tecnico, Universidade de Lisboa, Av. Rovisco Pais ,
1049-001 Lisboa, Portugal
E-mail: [email protected]
http://cqe.ist.utl.pt/personal_pages/pages/armando_pombeiro.php
Inorganic coordination compounds can act as electron-transfer mediators in electrocatalysis, with
energy saving and increased selectivity in comparison with direct electron-induced reactions.
Electrochemical methods play a relevant role in the study of such processes, what will be illustrated by
the electrochemical behaviour of Amavadin, an intriguing natural bare vanadium(IV) complex, present
in some toadstools, such as amanita muscaria, which acts as an electrocatalyst for the oxidation of
some biological thiols and behaves as an enzyme in this and other oxidation reactions, namely of
alkanes (as a peroxidase in their peroxidative oxidation and as a haloperoxidase in their peroxidative
halogenation). Amavadin and related vanadium complexes also efficiently catalyze the carboxylation of
alkanes to carboxylic acids.
These reactions are of significance in the field of functionalization of alkanes under environmentally
acceptable conditions, and the extension of the study to other inorganic coordination catalysts, e.g.,
based on copper or iron, either mononuclear complexes or heteropolynuclear assemblies, including
coordination polymers (MOFs) synthesized by self-assembly, will also be discussed, as well as the
mechanisms involved and the interesting role played by water. These catalytic systems are (or are
among) the most active ones so far reported for mild functionalization of alkanes.
Acknowledgments: The co-authors are gratefully acknowledged. The work has been partially
supported by the Foundation for Science and Technology (FCT), Portugal.
References
- Pombeiro, A.J.L. (Ed.), “Advances in Organometallic Chemistry and Catalysis” (The Silver/Gold Jubilee ICOMC
Celebratory Book), J. Wiley & Sons, 2014, Chapters 2, 3 and 22.
- Da Silva, J.A. L.; Fraústo da Silva, J.J.R.; Pombeiro, A.J.L. “Amavadin, a Vanadium Natural Complex: its Role
and Applications”, Coord. Chem. Rev., 2013, 257, 2388.
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Yoshiaki NISHIBAYASHI School of Engineering, The University of Tokyo Tokyo, Japan Education & Professional Position: 1991: B.Sc., Kyoto University
1993: M.Sc., Kyoto University
1995: Ph.D., Kyoto University
1995-2000: Assistant Professor, The University of Tokyo
2000-2005: Assistant Professor, Kyoto University
2005-present: Associate Professor, The University of Tokyo
Honors and Awards: 2001: Young Chemist Award of Chemical Society of Japan
2005: Minister Award for Distinguished Young Scientists, Japan
2012: Green & Sustainable Chemistry Honorable Award, Japan
2012: JSPS Prize for Distinguished Scientists, Japan
Scientific Interests: Studies on nitrogen fixation by using transition metal complexes and organic reactions catalyzed by
transition metal complexes.
Recent papers : 151 original papers and 46 reviews. Selected examples are as follows.
(1) Unique Behavior of Dinitrogen-Bridged Dimolybdenum Complexes Bearing Pincer Ligand towards
Catalytic Formation of Ammonia, H. Tanaka, K. Arashiba, S. Kuriyama, A. Sasada, K. Nakajima, K.
Yoshizawa, Y. Nishibayashi, Nature Communications, 5, 3737 (2014).
(2) Iron-Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Conditions ,
M. Yuki, H. Tanaka, K. Sasaki, Y. Miyake, K. Yoshizawa, Y. Nishibayashi, Nature Communications, 3,
1254 (2012).
(3) A Molybdenum Complex Bearing PNP-type Pincer Ligands Leads to the Catalytic Reduction of
Dinitrogen into Ammonia, K. Arashiba, Y. Miyake, Y. Nishibayashi, Nature Chemistry, 3, 120-125
(2011).
(4) A Non-metal System for Nitrogen Fixation, Y. Nishibayashi, M. Saito, S. Uemura, S. Takekuma, H.
Takekuma, Z. Yoshida, Nature, 428, 279-280 (2004).
(5) Bimetallic System for Nitrogen Fixation: Ruthenium-assisted Protonation of Coordinated N2 on
Tungsten with H2, Y. Nishibayashi, S. Iwai, M. Hidai, Science, 279, 540-542 (1998).
22
Molybdenum-Catalyzed Reduction of Molecular Dinitrogen
into Ammonia under Ambient Conditions
Yoshiaki NISHIBAYASHI Institute of Engineering Innovation, School of Engineering,
The University of Tokyo, 113-8656 Japan
Phone&FAX: +81-3-5841-1175
e-mail: [email protected] http://park.itc.u-tokyo.ac.jp/nishiba/
Synthesis of transition metal-dinitrogen complexes and stoichiometric transformation of their
coordinated dinitrogen into ammonia and hydrazine have so far been well investigated toward the goal
of achievement of nitrogen fixation under ambient conditions. After the first report on the catalytic
reaction by Schrock and co-worker,1 there is no example on the catalytic conversion of dinitrogen into
ammonia under ambient conditions. As an extension of our study,2 the dimolybdenum-dinitrogen
complex bearing PNP pincer ligand has been found to work as an effective catalyst for the formation of
ammonia from dinitrogen, where 52 equiv of amount of ammonia are produced based on the catalyst
(26 equiv of ammonia are produced based on the molybdenum atom of the catalyst).3-6
This is
another successful example of the catalytic and direct conversion of dinitrogen into ammonia under
ambient reaction conditions.7
1 Yandulov, D. V.; Schrock, R. R. Science 2003, 301, 76.
2 (a) Tanaka, H.; Sasada, A.; Kouno, T.; Yuki, M.; Miyake, Y.; Nakanishi, H.; Nishibayashi, Y.; Yoshizawa, K. J.
Am. Chem. Soc. 2011, 133, 3498. (b) Yuki, M.; Tanaka, H.; Sasaki, K.; Miyake, Y.; Yoshizawa, K.; Nishibayashi,
Y. Nature Communications 2012, 3, 1254.
3 Arashiba, K.; Miyake, Y.; Nishibayashi, Y. Nature Chemistry 2011, 3, 120.
4 (a) Arashiba, K.; Sasaki, K.; Kuriyama, S.; Miyake, Y.; Nakanishi, H.; Nishibayashi, Y. Organometallics 2012, 31,
2035. (b) Kinoshita, E.; Arashiba, K.; Kuriyama, S.; Miyake, Y.; Shimazaki, R.; Nakanishi, H.; Nishibayashi, Y.
Organometallics 2012, 31, 8437. (c) Arashiba, K.; Kuriyama, S.; Nakajima, K.; Nishibayashi, Y. Chem. Commun.
2013, 49, 11215. (d) Tanabe, Y.; Kuriyama, S.; Arashiba, K.; Miyake, Y.; Nakajima, K.; Nishibayashi, Y. Chem.
Commun. 2013, 49, 9290.
5 Tanaka, H.; Arashiba, K.; Kuriyama, S.; Sasada, A.; Nakajima, K.; Yoshizawa, K.; Nishibayashi, Y. Nature
Communications 2014, 5, 3737.
6 Kuriyama, S.; Arashiba, K.; Nakajima, K.; Tanaka, H.; Kamaru, N.; Yoshizawa, K.; Nishibayashi, Y. submitted.
7 Iron-catalyzed reaction has recently been reported by Peters and co-workers; Anderson, J. A.; Rittle, J.; Peters,
J. C. Nature 2013, 501, 81.
+ +ambient temperature and pressure
cat.
52 equiv of NH3 based on the catalyst!
2 NH36 eĞ 6 H+N2
N
N
N
N
N
N
Mo
N
N
N
N
NP
P
N
P
P
Mo
P = PtBu2
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Luisa De Cola Institute de Science et d'Ingénierie
Supramoléculaires (ISIS), Université de Strasbourg
and KIT, Germany ([email protected])
Education:
Since 1 September 2013 Full Professor (Class Exceptionnelle), and AXA chair of Supramolecular
and Biomaterial Chemistry, at ISIS, University of Strasbourg.
1978 - 1983 Laurea in Chemistry summa cum laude, University of Messina (Italy)
1984 - 1986 Postdoctoral fellow (NIH) at the Virginia Commonwealth University, Richmond, USA
1990 - 1998 Assistant Professor University of Bologna (Italy).
1998 - 2004 Full Professor, University of Amsterdam (the Netherlands)
2005 - 2012 Full Professor (C4) in Physics and Chemistry, University of Münster, (Germany)
2012 - University of Strasbourg/ISIS AXA chair in Supramolecular and Biomaterials Chemistry
2012 - Adjunct Scientist at the Karlsruher Institut für Technologie (KIT), Germany
Selected recent awards and Professional Appointments:
1995 Federchimica National Prize "per un futuro intelligente (for a smart future)".
1995 International Prize of the European Photochemistry Association "Grammaticakis Neumann"
2003-07 Member of the Advisory Board for the Chemistry Department, Imperial College of London
2009 European Research Council, ERC Advanced Grant Award
2011 IUPAC prize for the most distinguished women in the field of chemistry and chemical
engineering
2012 Gutenberg Chair Award
2013 Member of the Academia Europeae
2014 - Chevalier de la Légion d’Honneur appointed by the President of the Republic of France,
François Hollande
2014 - Member of the German Academy of Sciences, Leopoldina
2014 - International Prize for Chemistry from the Academia dei Lincei (Tartufari Prize)
Scientific Interests : a) luminescent and electro-luminescent materials for optical and
electroluminescent devices; b) nanomaterials for imaging diagnostics and therapy; c) self -assembly in
solution, solid and in confined spaces.
Recent papers : L. De Cola, W.G. van der Wiel et al. "Ultra-high magnetoresistance at room
temperature in molecular wires” Science, 2013, 341, 257-260.
M. Mauro, A. Aliprandi, D. Septiadi, N. S. Kehr, L. De Cola "When self -assembly meets biology:
luminescent platinum complexes for imaging applications" Chem. Soc. Rev., 2014, 43, 4144-4166.
N. S. Kehr, B. Ergün, H. Lülf, L. De Cola "Spatially controlled channel entrances functionalisation of
zeolites L" Adv. Mat., 2014, 26, 3248–3252.
M. Mauro, L. De Cola et al. "Self-assembling a neutral platinum(II) complex into highly emitting
microcrystalline fibers through metallophilic interactions" Chem. Commun. 2014, 50, 7269-7272
A. Bertucci, H. Lülf, D. Septiadi, A. Manicardi, R. Corradini, L. De Cola "Intracellular delivery of Peptide
Nucleic Acid and organic molecules using zeolite-L nanocrystals" Adv. Health. Mater., 2014, in press.
H. Lülf, A. Bertucci, D. Septiadi, R. Corradini, L. De Cola "Multifunctional inorganic nanocontainers for
DNA and drug delivery into living cells" Chem. Eur. J., 2014 in press, cover of the issue.
24
Dynamic and hybrid materials. Properties and applications
Luisa DE COLA
Institute de Science et d'Ingénierie Supramoléculaires (I.S.I.S.),
Université de Strasbourg and KIT, Germany
Phone: +33(0)368855220, Fax: +33(0)368855242
e-mail: [email protected] http://decola.u-strasbg.fr
Dynamic systems that can undergo reversible processes are of great interest for the development of
new materials, sensors, biolabels…. The talk will illustrate some of the recent results on soft structures
based on metal complexes able to aggregate in fibers, gels and soft mechanochromic materials. The
use of platinum complexes as building block for luminescent reversible piezochromic and
mechanochromic materials will be illustrated. The emission of the compounds can be tuned by an
appropriate choice of the
coordinated ligands as well as
of their aggregation in different
structures. The formation of soft
assemblies allows the tuning of
the emission color, by pressure
and temperature leading to a
new class of materials
possessing reversible properties.
Functional systems can also be created using inert or active inorganic nanocontainers such as
microporous and mesoporous silica based nanoparticles. The different functionalization of their
surface will be discussed, in particular with the aim to show that the particles can be decorated with
different functional groups including biocompatible molecules and are able to perfom drug and
oligonucleotide delivery inside the cell. The delivery can be probed by kinetic analyses after the
nanoparticles internalization. In particular using confocal fluorescent microscopy it is possible to follow
the release of each single component as well as the positioning of the nanoconta iners in real time and
space. Such achievement allows us to study the fate of the different units and their release time. Also
it will be shown how the molecules entrapped in the ordered channels can become active components.
The alignment of electroactive molecules inside the narrow channels of a zeolite L, resulted in the
formation of molecular wires. The molecular wire length is tunable between 30 and 100 nm and
electrical measurements on the 1D assemblies were performed. Finally an ultra-high (> 2000%)
roomtemperature magnetoresistance was observed applying only a few mT.
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Kazuyuki TATSUMI Research Center for Materials Science, Nagoya University
Education: 1971 B.Sc., 1976 Ph.D. from Osaka University
Professional Career:
1977-1979 Postdoctoral Fellow, Texas A&M University
1979-1982 Postdoctoral Fellow, Cornell University (R. Hofffmann)
1982-1991 Assistant Professor, Osaka University
1991-1994 Associate Professor, Osaka University
1994-2013 Professor, Nagoya University
2013 - Designated Professor, Nagoya University
Scientific Activities (2007 -):
2005-2011 Member of Council for Science and Technology, MEXT, Japan
2006-2010 Vice Chair: International Organizing Committee (Pacifichem 2010)
2008-2009 President: Division II (Inorganic Chemistry Division), IUPAC
2008 - Council Member: Science Council of Japan
2011 - Head Investigator: Grant-in-Aid for Specifically Promoted Research of MEXT,
“Bioinorganic Chemistry of Oxidoreductases having Unique Active Site Clusters”
2012-2013 President: IUPAC
2013 - Vice Chair: Division III, Science Council of Japan
Major Honors:
2004 Humboldt Award (Av Humboldt Foundation, Germany)
2006 The Chemical Society of Japan Award
2011 Honorary Doctorate, University of Münster (Germany)
2011 The Eugen and Ilse Seibold Prize (DFG, Germany)
2013 The Prize for Science and Technology (MEXT, Japan)
2013 The Japan Academy Prize
Scientific Interests : 1) Transition Metal Chalcogenide Chemistry and Theoretical Inorganic Chemistry
2) Coordinatively Unsaturated Organometallic Complexes and Activation of Small Molecules
3) Synthesis of the Cluster Active Sites of Metalloenzymes.
Recent papers : (1) Z. Li, Y. Ohki, K. Tatsumi, J. Am. Chem. Soc., 2005, 27, 8950-8951.
(2) Y. Ohki, Y. Ikagawa, K. Tatsumi, J. Am. Chem. Soc., 2007, 129, 10457-10465.
(3) Y. Ohki, N. Tokitoh, M. Katada, K. Tatsumi, et al., J. Am. Chem. Soc., 2009, 131, 13168.
(4) M. Ito, T. Matsumoto, K. Tatsumi, et al., Proc. Nat. Acad. Sci. (USA), 2009, 106, 11862-11866.
(5) T. Matsumoto, K. Tatsumi, N. Suganuma, et al., Nature, 2009, 462, 514-518.
(6) Y. Ohki, K. Tatsumi, et al., Proc. Nat. Acad. Sci. (USA), 2010, 107, 3994-3997.
(7) Y. Ohki, K. Tatsumi, et al., Proc. Nat. Acad. Sci. (USA), 2011, 108, 12635-12640.
26
Organometallic Chemistry of Reductases
– A Clue to Building a Future Sustainable Society –
Kazuyuki Tatsumi
Research Center for Materials Science, Nagoya University,
Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan,
Phone : +81-52-789-2474, Fax: +81-52-789-2943,
E-mail: [email protected]
The research on reductases and related metalloenzymes has progressed rapidly in recent years,
unraveling novel structures and functions of the cluster active centers and greatly expanding the
established knowledge of chemistry. Newly discovered reductases show remarkable activities,
exemplified by nitrogenases catalyzing the reduction of dinitrogen into ammonia, hydrogenases
reversibly converting dihydrogen into protons and electrons, CO-dehydrogenases generating protons
and electrons from CO and water, and acetyl CoA synthase forming acetyl CoA from carbon monoxide,
methyl cobalamin, and coenzyme A (CoA). The brilliant functions of these enzymes stand out as a
microcosm of the “the mystery of nature” that modern science should strive to understand, and
therefore the importance of chemical research on the structure-function relationship of the active sites
has been recognized.
These reductases promote “organometallic reactions” in nature. For instance, the function of CO -
dehydrogenases is equivalent to the so-called water-gas-shift reaction in organometallic chemistry, and
acetyl CoA synthase involves the CO insertion into a Ni-CH3 bond in its function. Interestingly
hydrogenases contain a typical organometallic iron-carbonyls in their active centers. The active sites of
reductases are made of unprecedented transition metal sulfide clusters, which have been long-standing
targets of synthetic chemists and are extremely challenging due to the instability and complexity of the
cluster structures.
This presentation will focus on our recent study of chemical synthesis of the nitrogenase active sites
and their electronic properties.
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Centre National de la Recherche Scientifique 3, Rue Michel-Ange 75794, Paris, France Tel: +33(0)3 68 85 00 00 www.cnrs.fr/ Université de Strasbourg 4 rue Blaise Pascal CS 90032 F-67081 Strasbourg cedex Tel: +33(0)3 68 85 00 00 www.unistra.fr/ JSPS Strasbourg Office Maison universitaire France Japon 42a, avenue de la Forêt Noire 67000 Strasbourg, France Tel: +33(0)3 68 85 20 17 [email protected] http://jsps.unistra.fr/