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Unconventional Approaches to the Activation of Dihydrogen (FOR 1175) (D-A-CH/LAE)

English title Unconventional Approaches to the Activation of Dihydrogen (FOR 1175) (D-A-CH/LAE)
Applicant Berke Heinz
Number 126711
Funding scheme Project funding (special)
Research institution Institut für Chemie Universität Zürich
Institution of higher education University of Zurich - ZH
Main discipline Inorganic Chemistry
Start/End 01.02.2010 - 30.06.2014
Approved amount 1'254'026.00
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Keywords (6)

Hydrogen, Activation, ; Homogeneous catalysis, Hydrogenation, ; Metal-free Hydrogenation, ; Transition metal catalyst; Ionic Hydrogenation; Transfer Hydrogenation

Lay Summary (English)

Lead
Lay summary
LeadIn a binational Swiss-German cooperation this project addresses fundamental aspects of hydrogen chemistry and developments emphasizing the timely aspects of “metal-free” and “ionic hydrogenation” catalyses proceeding with heterolytic splitting of the H-H bond.Hydrogen chemistry has recently gained importance in conjunction with its potential role as a “clean” energy carrier and its connection to chemical hydrogen storage. A conceptually new, basic research approach to hydrogen chemistry was chosen to solve the remaining chemical enigma of hydrogen transformations. For decades hydrogen research focused mainly on developments of Wilkinson transition metal catalyses with the characteristics of a homolytic splitting of H2. Major drawbacks of this chemistry were the use of noble metal catalysts and the preference for reactions with unpolar unsaturated molecules. These drawbacks are thought to be overcome by utilization of recently emerged aspects of hydrogenations splitting H2 by heterolysis, which are cumulatively denoted as “ionic hydrogenations” and are transition metal or main group element “metal-free” catalyzed. Polar transfer hydrogenations, operating on the basis of a simultaneously occurring double H transfers, are also studied in this project.A comprehensive fundamental approach to hydrogen chemistry is sought consisting of developments for “ionic hydrogenations” and polar transfer hydrogenations, preferably in catalytic form with emphasis on “metal-free” catalysis or very efficient noble metal catalysis. A broad search for new hydrogen related catalyses builds the chemical platform for this Swiss-German cooperation.In conjunction with the vision of dihydrogen as a “clean” future energy carrier and the involvement of dihydrogen reactivity in chemical hydrogen storage materials, this bi-national collaborative project attains considerable socialrelevance. The project would like to contribute to an ultimate profound understanding of dihydrogen chemistry exploring the missing facets of polar and “metal-free” hydrogen and hydrogen related catalyses. Respective new insights are thought to lay the grounds for future chemical developments in hydrogen technology.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP)
Heift Dominikus, Benko Zoltan, Gruetzmacher Hansjoerg (2014), Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP), in DALTON TRANSACTIONS, 43(2), 831-840.
Homogeneous Hydrogenation of Nitriles Catalyzed by Molybdenum and Tungsten Amides
Chakraborty Subrata, Berke Heinz (2014), Homogeneous Hydrogenation of Nitriles Catalyzed by Molybdenum and Tungsten Amides, in ACS CATALYSIS, 4(7), 2191-2194.
Synthesis of functionalized pyridinium salts bearing a free amino group
Auth Johanna, Mauleon Pablo, Pfaltz Andreas (2014), Synthesis of functionalized pyridinium salts bearing a free amino group, in ARCIVOC, 2014(3), 154-168.
The Color of Complexes and UV-vs Spectroscopy as an Analytical Tool of Alfred Werner's Group at the University of Zurich
Fox Thomas, Berke Heinz (2014), The Color of Complexes and UV-vs Spectroscopy as an Analytical Tool of Alfred Werner's Group at the University of Zurich, in CHIMIA, 68(5), 307-311.
A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures.
Rodríguez-Lugo Rafael E, Trincado Mónica, Vogt Matthias, Tewes Friederike, Santiso-Quinones Gustavo, Grützmacher Hansjörg (2013), A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures., in Nature chemistry, 5(4), 342-7.
Catalytic CO2 activation assisted by rhenium hydride/B(C 6F5)3 frustrated Lewis pairs - Metal hydrides functioning as FLP bases
Jiang Y, Blacque O, Fox T, Berke H (2013), Catalytic CO2 activation assisted by rhenium hydride/B(C 6F5)3 frustrated Lewis pairs - Metal hydrides functioning as FLP bases, in Journal of the American Chemical Society, 135(20), 7751-7760.
Catalytic CO2 Activation Assisted by Rhenium Hydride/B(C6F5)(3) Frustrated Lewis Pairs-Metal Hydrides Functioning as FLP Bases
Jiang Yanfeng, Blacque Olivier, Fox Thomas, Berke Heinz (2013), Catalytic CO2 Activation Assisted by Rhenium Hydride/B(C6F5)(3) Frustrated Lewis Pairs-Metal Hydrides Functioning as FLP Bases, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135(20), 7751-7760.
Catalytic CO2 Activation Assisted by Rhenium Hydride/B(C6F5)(3) Frustrated Lewis Pairs-Metal Hydrides Functioning as FLP Bases
Jiang Yanfeng, Blacque Olivier, Fox Thomas, Berke Heinz (2013), Catalytic CO2 Activation Assisted by Rhenium Hydride/B(C6F5)(3) Frustrated Lewis Pairs-Metal Hydrides Functioning as FLP Bases, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135(20), 7751-7760.
Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity
Berke Heinz, Jiang Yanfeng, Yang Xianghua, Jiang Chunfang, Chakraborty Subrata, Landwehr Anne (2013), Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity, in FRUSTRATED LEWIS PAIRS II: EXPANDING THE SCOPE, 334, 27-57.
Coexistence of lewis Acid and base functions: a generalized view of the frustrated lewis pair concept with novel implications for reactivity.
Berke Heinz, Jiang Yanfeng, Yang Xianghua, Jiang Chunfang, Chakraborty Subrata, Landwehr Anne (2013), Coexistence of lewis Acid and base functions: a generalized view of the frustrated lewis pair concept with novel implications for reactivity., in Topics in current chemistry, 334, 27-57.
Coordination Properties of Multidentate Phosphanylborane Ligands in Tungsten Nitrosyl Complexes
Jana Rajkumar, Blacque Olivier, Jiang Yanfeng, Berke Heinz (2013), Coordination Properties of Multidentate Phosphanylborane Ligands in Tungsten Nitrosyl Complexes, in EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (18), 3155-3166.
Coordination properties of multidentate phosphanylborane ligands in tungsten nitrosyl complexes
Jana R, Blacque O, Jiang Y, Berke H (2013), Coordination properties of multidentate phosphanylborane ligands in tungsten nitrosyl complexes, in European Journal of Inorganic Chemistry, (18), 3155-3166.
Direct Amidation of Aldehydes with Primary Amines under Mild Conditions Catalyzed by Diolefin-Amine-Rh-I Complexes
Rodriguez-Lugo Rafael E., Trincado Monica, Gruetzmacher Hansjoerg (2013), Direct Amidation of Aldehydes with Primary Amines under Mild Conditions Catalyzed by Diolefin-Amine-Rh-I Complexes, in CHEMCATCHEM, 5(5), 1079-1083.
Isotope ratio determination of objects in the field by portable laser ablation sampling and subsequent multicollector ICPMS
Glaus Reto, Dorta Ladina, Zhang Zhiguo, Ma Qinglin, Berke Heinz, Guenther Detlef (2013), Isotope ratio determination of objects in the field by portable laser ablation sampling and subsequent multicollector ICPMS, in JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, 28(6), 801-809.
Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B-O Bond Formation
Jana Rajkumar, Chakraborty Subrata, Blacque Olivier, Berke Heinz (2013), Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B-O Bond Formation, in EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013(26), 4574-4584.
Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B-O Bond Formation
Jana Rajkumar, Chakraborty Subrata, Blacque Olivier, Berke Heinz (2013), Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B-O Bond Formation, in EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013(26), 4574-4584.
Stepwise Construction of an Iron-Substituted Rigid-Rod Molecular Wire: Targeting a Tetraferra-Tetracosa-Decayne
Lissel Franziska, Fox Thomas, Blacque Olivier, Polit Walther, Winter Rainer F., Venkatesan Koushik, Berke Heinz (2013), Stepwise Construction of an Iron-Substituted Rigid-Rod Molecular Wire: Targeting a Tetraferra-Tetracosa-Decayne, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135(10), 4051-4060.
Bifunctional Rhenium Complexes for the Catalytic Transfer-Hydrogenation Reactions of Ketones and Imines
Landwehr Anne, Dudle Balz, Fox Thomas, Blacque Olivier, Berke Heinz (2012), Bifunctional Rhenium Complexes for the Catalytic Transfer-Hydrogenation Reactions of Ketones and Imines, in CHEMISTRY-A EUROPEAN JOURNAL, 18(18), 5701-5714.
Improvement in the efficiency of an OrganoMetallic Fuel Cell by tuning the molecular architecture of the anode electrocatalyst and the nature of the carbon support
Bevilacqua M., Bianchini C., Marchionni A., Filippi J., Lavacchi A., Miller H., Oberhauser W., Vizza F., Granozzi G., Artiglia L., Annen S. P., Krumeich F., Gruetzmacher H. (2012), Improvement in the efficiency of an OrganoMetallic Fuel Cell by tuning the molecular architecture of the anode electrocatalyst and the nature of the carbon support, in ENERGY & ENVIRONMENTAL SCIENCE, 5(9), 8608-8620.
Nitrosobenzene as a hydrogen acceptor in rhodium catalysed dehydrogenation reactions of alcohols: synthesis of aldehydes and azoxybenzenes.
Annen Samuel P, Grützmacher Hansjörg (2012), Nitrosobenzene as a hydrogen acceptor in rhodium catalysed dehydrogenation reactions of alcohols: synthesis of aldehydes and azoxybenzenes., in Dalton transactions (Cambridge, England : 2003), 41(46), 14137-45.
Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors
Yang Xianghua, Fox Thomas, Berke Heinz (2012), Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors, in ORGANIC & BIOMOLECULAR CHEMISTRY, 10(4), 852-860.
Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors
Yang XH, Fox T, Berke H (2012), Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors, in ORGANIC & BIOMOLECULAR CHEMISTRY, 10(4), 852-860.
The decline of the early Neolithic population center of 'Ain Ghazal and corresponding earth-surface processes, Jordan Rift Valley
Zielhofer Christoph, Clare Lee, Rollefson Gary, Waechter Stephan, Hoffmeister Dirk, Bareth Georg, Roettig Christopher, Bullmann Heike, Schneider Birgit, Berke Hubert, Weninger Bernhard (2012), The decline of the early Neolithic population center of 'Ain Ghazal and corresponding earth-surface processes, Jordan Rift Valley, in QUATERNARY RESEARCH, 78(3), 427-441.
1,3-Bis(pyridin-2-yl)-1H-benzimidazol-3-ium tetrafluoridoborate
Grieco G, Blacque O, Berke H (2011), 1,3-Bis(pyridin-2-yl)-1H-benzimidazol-3-ium tetrafluoridoborate, in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 67, 2066-805.
A mild and efficient rhenium-catalyzed transfer hydrogenation of terminal olefins using alcoholysis of amine-borane adducts as a reducing system
Dong HL, Berke H (2011), A mild and efficient rhenium-catalyzed transfer hydrogenation of terminal olefins using alcoholysis of amine-borane adducts as a reducing system, in JOURNAL OF ORGANOMETALLIC CHEMISTRY, 696(9), 1803-1808.
Amino olefin nickel(I) and nickel(0) complexes as dehydrogenation catalysts for amine boranes
Vogt M, de Bruin B, Berke H, Trincado M, Grutzmacher H (2011), Amino olefin nickel(I) and nickel(0) complexes as dehydrogenation catalysts for amine boranes, in CHEMICAL SCIENCE, 2(4), 723-727.
Ammonia borane as a metal free reductant for ketones and aldehydes: a mechanistic study
Yang XH, Fox T, Berke H (2011), Ammonia borane as a metal free reductant for ketones and aldehydes: a mechanistic study, in TETRAHEDRON, 67(37), 7121-7127.
Ammonia borane as a metal free reductant for ketones and aldehydes: a mechanistic study
Yang Xianghua, Fox Thomas, Berke Heinz (2011), Ammonia borane as a metal free reductant for ketones and aldehydes: a mechanistic study, in TETRAHEDRON, 67(37), 7121-7127.
Chiral dihydrobenzo[1,4]oxazines as catalysts for the asymmetric transfer-hydrogenation of alpha,beta-unsaturated aldehydes
Ebner C, Pfaltz A (2011), Chiral dihydrobenzo[1,4]oxazines as catalysts for the asymmetric transfer-hydrogenation of alpha,beta-unsaturated aldehydes, in TETRAHEDRON, 67(52), 10287-10290.
Facile metal free regioselective transfer hydrogenation of polarized olefins with ammonia borane
Yang XH, Fox T, Berke H (2011), Facile metal free regioselective transfer hydrogenation of polarized olefins with ammonia borane, in CHEMICAL COMMUNICATIONS, 47(7), 2053-2055.
Heterolytic Cleavage of H-2 by Frustrated B/N Lewis Pairs
Jiang CF, Blacque O, Fox T, Berke H (2011), Heterolytic Cleavage of H-2 by Frustrated B/N Lewis Pairs, in ORGANOMETALLICS, 30(8), 2117-2124.
Metal-ligand cooperation in the catalytic dehydrogenative coupling (DHC) of polyalcohols to carboxylic acid derivatives.
Trincado Mónica, Kühlein Klaus, Grützmacher Hansjörg (2011), Metal-ligand cooperation in the catalytic dehydrogenative coupling (DHC) of polyalcohols to carboxylic acid derivatives., in Chemistry (Weinheim an der Bergstrasse, Germany), 17(42), 11905-13.
Probing the catalytic potential of chloro nitrosyl rhenium(I) complexes
Jiang YF, Blacque O, Berke H (2011), Probing the catalytic potential of chloro nitrosyl rhenium(I) complexes, in DALTON TRANSACTIONS, 40(11), 2578-2587.
Reversible, metal-free hydrogen activation by frustrated Lewis pairs
Jiang CF, Blacque O, Fox T, Berke H (2011), Reversible, metal-free hydrogen activation by frustrated Lewis pairs, in DALTON TRANSACTIONS, 40(5), 1091-1097.
A biologically inspired organometallic fuel cell (OMFC) that converts renewable alcohols into energy and chemicals.
Annen Samuel P, Bambagioni Valentina, Bevilacqua Manuela, Filippi Jonathan, Marchionni Andrea, Oberhauser Werner, Schönberg Hartmut, Vizza Francesco, Bianchini Claudio, Grützmacher Hansjörg (2010), A biologically inspired organometallic fuel cell (OMFC) that converts renewable alcohols into energy and chemicals., in Angewandte Chemie (International ed. in English), 49(40), 7229-33.
Activation of terminal alkynes by frustrated lewis pairs
Jiang C, Blacque O, Berke H (2010), Activation of terminal alkynes by frustrated lewis pairs, in Organometallics, 29(1), 125-133.
Catalytic Aerobic Dehydrogenative Coupling of Primary Alcohols and Water to Acids Promoted by a Rhodium(I) Amido N-Heterocyclic Carbene Complex
Annen Samuel, Zweifel Theo, Ricatto Federica, Gruetzmacher Hansjoerg (2010), Catalytic Aerobic Dehydrogenative Coupling of Primary Alcohols and Water to Acids Promoted by a Rhodium(I) Amido N-Heterocyclic Carbene Complex, in CHEMCATCHEM, 2(10), 1286-1295.
Conceptual approach to the reactivity of dihydrogen
Berke H (2010), Conceptual approach to the reactivity of dihydrogen, in ChemPhysChem, 11(9), 1837-1849.
Domino rhodium/palladium-catalyzed dehydrogenation reactions of alcohols to acids by hydrogen transfer to inactivated alkenes.
Trincado Mónica, Grützmacher Hansjörg, Vizza Francesco, Bianchini Claudio (2010), Domino rhodium/palladium-catalyzed dehydrogenation reactions of alcohols to acids by hydrogen transfer to inactivated alkenes., in Chemistry (Weinheim an der Bergstrasse, Germany), 16(9), 2751-7.
Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 - Dihydrogen bonding and H2 formation with protic donors
Avramović N, Höck J, Blacque O, Fox T, Schmalle HW, Berke H (2010), Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 - Dihydrogen bonding and H2 formation with protic donors, in Journal of Organometallic Chemistry, 695(3), 382-391.
10. Bifunctional Rhenium Complexes for the Catalytic Transfer-Hydrogenation Re-actions of Ketones and Imines
A. Landwehr, B. Dudle, T. Fox, O. Blacque, H. Berke, 10. Bifunctional Rhenium Complexes for the Catalytic Transfer-Hydrogenation Re-actions of Ketones and Imines, in Chemistry-A European Journal.

Associated projects

Number Title Start Funding scheme
139173 Single Crystal Diffractometer with Cu/Mo Microsource 01.12.2011 R'EQUIP

Abstract

A binational Swiss-German cooperation project on dihydrogen (H2) chemistry has been set up.Dihydrogen chemistry has recently gained major importance in conjunction with the advent of hydrogen technology and its potential application as a future energy carrier. The development of hydrogen technology requires the use of sophisticated hydrogen chemistry. However, various aspects of hydrogen chemistry related to technology remained to be addressed such as a comprehensive fundamental picture of hydrogen reactivity and developments to circumvent as much as possible noble metal chemistry.A conceptually new, basic research approach to hydrogen chemistry has been chosen to solve the remaining chemical problems of chemical transformations, which comprise processes involving hydrogenations /dehydrogenations and transfer hydrogenations occurring as 1,2-additions/1,2-eliminations or type II dyotropic rearrangements. Under ambient conditions proper hydrogen reactivity requires support from mediating reaction centres, which normally turn out to be catalytic reaction centres showing repetitive turnovers of the molecules. For decades related research focussed on developments of Wilkinson type transition metal catalyses with the characteristics of oxidative addition of H2 to the transition metal centres steps occurring with its formal homolytic splitting. Major drawbacks of this chemistry are however the quite limiting conditions of a “must” to use noble metal catalysts and the strong preference of Wilkinson type catalysts for reactions with mostly relatively unpolar or less polar unsaturated molecules. These drawbacks are envisaged to be overcome by further developments and utilizations of recently emerged aspects of hydrogenation/dehydrogenation and transfer hydrogenation catalysts splitting the H2 molecule formally in a heterolytic fashion. Hydrogenations using heterolytic splitting of H2 are cumulatively denoted as “ionic hydrogenations” and are to the main part also transition metal catalyzed. Only very recently a new type of heterolytic H2 splitting was discovered with main group element compounds and respective “ionic hydrogenation” chemistry was also found to exist. It is denoted as “metal-free”. Transfer hydrogenations are also related to “ionic hydrogenations“ operating on the basis of simultaneously occurring double H transfers, but do not involve hydrogen directly. The catalytic potential of these transfer hydrogenations has yet not fully been exploited. In summary this means that comprehensive chemical developments for “ionic hydrogenations” and transfer hydrogenations are lacking and were therefore taken as targets of this project. A broad search for new hydrogenation catalyses builds the chemical platform for cooperation within this project.Taking advantage of synergistic effects and mutual stimulations the Swiss-German cooperation consists of up with five organometallic chemistry groups, one physical chemistry group and one theoretical group, which set out to study the above listed fundamental aspects of hydrogenation chemistry together with their possible utilizations in form of efficient catalyses. Two groups (Erker, Pfaltz) of the team will get fully involved in the exploration and exploitation of a “metal-free” H2 chemistry using main group elements or organic heteropolar hydrogen splitting systems; two other groups will get partly involved in “metal-free” hydrogen chemistry (Berke, Rieger). Three groups participate in the team in a related “metal-containing” H2 chemistry utilizing transition metal centres (Berke, Grützmacher, Rieger). One group will attempt to trace new intermediates of hydrogen chemistry by sophisticated spectroscopies low-temperature matrices (Sander). Another group will lay the foundation for exact electronic views of the molecules and chemical transformations appearing in this project by application of accurate theoretical calculations (Grimme).Coherent research strategies and unifying views of hydrogen chemistry are the basis for proper concepts within this project. Comprehensiveness in the coverage is combined with academic depth in the explorations of the various chemical aspects. Besides these fundamental chemical aspects, a high degree of sophistication is sought to be invested in the application of sophisticated analytical tools.
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