个人简介

B.Sc., Tel Aviv University, Israel, 2000 Ph.D., Tel Aviv University, Israel, 2006 Postdoctoral Associate, Harvard University, 2006-2009 Postdoctoral Fellow, MIT, 2009-2011

研究领域

Synthetic inorganic and organometallic chemistry/bioinorganic chemistry/ligand design/catalysis/small molecule activation

We are a synthetic inorganic group with research interests in the fields of organometallic chemistry, bioinorganic chemistry, and catalysis. Our projects are focused on the activation of small molecules crucial to the fields of energy and the environment. Our research involves ligand design, coordination chemistry with transition and main-group elements, and reactivity studies. Our first project focuses on dinuclear metal centers capable of cooperative reactivity in the activation of heteroallenes. The motivation for this research comes from the need to develop efficient catalysts for CO2 reduction and storage. Due to its low price, high abundance, and detrimental environmental effects, CO2 is an attractive C1 building block for the synthesis of chemicals or fuels. Two reactions of CO2 are of interest to us: reductive coupling to give oxalate, and the reductive splitting to yield CO and [O]. Reductive coupling of CO2 provides the most direct pathway toward transformation of CO2 to C2 chemicals, and we are seeking to unravel key factors in the molecular chemistry of CO2 that enable its reductive coupling. Our hypothesis is that the C-C bond formation in the transformation of CO2 to oxalate can be facilitated via cooperative intramolecular catalysis at dinuclear metal centers engineered to undergo facile one-electron oxidation each. Oxalate is expected to bridge two metal centers, and the dinuclear topology of the catalyst should template its formation. We have synthesized two bimetallic platforms capable of binding oxalate inside the intramolecular cavity and are studying their catalytic reactivity. We are also designing bimolecular catalysts for the reductive splitting of CO2 and other heteroallenes. Reductive splitting provides a direct path from CO2 toward liquid fuels. Nature employs a heterobimetallic system at the active site of Ni/Fe CODH to split CO2. We are exploring various homo- and heterobimetallic systems capable of carrying out the required two-electron reduction cooperatively. Our second project involves the chemistry of low-coordinate first-row transition metal and main-group complexes containing very bulky alkoxide ligands. We are specifically targeting two-coordinate M(OR)2 species and three-coordinate M(OR)2(=X) species (M = Mn-Ni). The combination of high electronegativity and strong π-donor capability of the oxygen donor makes multiply-bonded ligands X (X = NR, N, O) at the mid- and late transition metals platforms strongly oxidizing. We are investigating the potential of these species as platforms for X group insertion into C-H bonds to form C-X-H products. We are also synthesizing low-valent main-group compounds coordinated by the alkoxide ligands, and studying their properties

近期论文

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Bheemaraju A.; Beattie, J. W.; Tabasan, E. G.; Martin, P. D.; Lord, R. L.; Groysman, S. Steric and Electronic Effects in the Formation and Carbon Disulfide Reactivity of Dinuclear Nickel Complexes Supported by Bis(iminopyridine) Ligands. Organometallics 2013, In Press A. Bheemaraju, J. W. Beattie, R. L. Lord, P. D. Martin, S. Groysman Carbon Disulfide Binding at Dinuclear and Mononuclear Nickel Complexes Ligated by a Redox-active Ligand: Iminopyridine Serving as an Accumulator of Redox Equivalents for the Activation of Heteroallenes. Chem. Commun. 2012, 48, 9595. A. Bheemaraju, R. L. Lord, P. M黮ler, S. Groysman Difference in the Reactivities of H- and Me-Substituted Dinucleating Bis(iminopyridine) Ligands with Nickel(0) Organometallics 2012, 31, 2120. S. Groysman, D. Villagr醤, D. E. Freedman, D. G. Nocera Dinitrogen Binding at Vanadium in the Tris(alkoxide) Ligand Environment Chem. Commun. 2011, 47, 10242. S. Groysman, D. Villagr醤, D. G. Nocera Pseudo-tetrahedral d0, d1 and d2 Metal-Oxo Cores Within a Tris(alkoxide) Platform Inorg. Chem. 2010, 49, 10759. S. Groysman, R. H. Holm A Series of Mononuclear Quasi-Two-Coordinate Copper(I) Complexes Employing a Sterically Demanding Thiolate Ligand Inorg. Chem. 2009, 48, 621.