个人简介

1994 B.S. Southern Illinois University at Edwardsville 1998 Ph.D. Texas A&M University 1998-2000 Alexander von Humboldt Postdoctoral Fellow Max-Planck Institut für Strahlenchemie

研究领域

Inorganic Chemistry, Metal-thiolates, ligand-based reactivity, inorganic synthesis

Research in the Grapperhaus Group focuses on the inorganic and bioinorganic chemistry of transition metal-thiolates. Transition metal-thiolates display variable reactivities that are dependent on the identity of the metal, the thiolate substituent group, and the covalency of the metal-sulfur bond. Our research seeks to identify and exploit these factors for the design of systems with synthetic or industrial utility. Specifically, we are interested systems that support reactive metal-coordinated thiyl radicals or that serve as artificial mimics of the enzyme nitrile hydratase. The research experience in the Grapperhaus group encompasses many complimentary approaches and techniques. Our investigations combine synthesis, reactivity, computation, spectroscopy, crystallography and electrochemistry. Undergraduate and graduate students develop a broad based approach to research.

近期论文

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"Reinvestigation of the first structurally characterized metal-coordinated sulfenic acid complex" Chauhan, R.; Mashuta, M. S.; Grapperhaus, C. A. Inorg. Chem. Commun. 2013, 37, 186-188 "Addition of polysubstituted alkenes, aromatic alkynes, and dienes to a metal-stabilized thiyl radical via carbon-sulfur bond formation: Electrochemical, chemical, and computational investigations" Sampson, K. O.; Kumar, D.; Mashuta, M. S.; Grapperhaus, C. A. Inorg. Chim. Acta 2013, 408, 1-8 "Probing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry" Lu, M.; Campbell, J. L.; Chauhan, R.; Grapperhaus, C. A. ; Chen, H. J. Am. Soc. Mass. Spec. 2013, 24, 502-512 "Bioinspired catalytic nitrile hydration by dithiolato, sulfinato/thiolato, and sulfenato/sulfinato ruthenium complexes" Kumar, D.; Masitas, C. A.; Tran, T. N.; Grapperhaus, C. A. Chem. Commun. 2013, 294–296 "Selective and Reversible Base-Induced Elimination of a Ruthenium Dithioether Yields a Vinyl Metallosulfonium Complex" Chauhan, R.; Mashuta, M. S.; Grapperhaus, C. A. Inorg. Chem. 2012, 51, 7913–7920 "Influence of Sequential Thiolate Oxidation on a Nitrile Hydratase Mimic Probed by Multiedge X-ray Absorption Spectroscopy" Shearer, J.; Callant, P. E.; Masistas, C. A.; Grapperhaus, C. A. Inorg. Chem. 2012, 51, 6032-6045 "Alkyne addition to a metal-stabilized thiyl radical: Carbon-sulfur bond formation between 1-octyne and [Ru(SP)3]+" Ouch, K.; Mashuta, M. S.; Grapperhaus, C. A. Eur. J. Inorg. Chem. 2012, 475-478 "Kinetic study of nickel-thiolate oxygenation by hydrogen peroxide. Implications for nickel-containing superoxide dismutase" Herdt, D. R.; Grapperhaus, C. A. Dalton Trans. 2012, 41, 364-366 "N-(2-formyl-1-methylimidazol-4-yl)-2,2-dimethylpropanamide: A versatile reagent for preparing imidazole-amine ligands with variable second-coordination spheres" Cheruzel, L. E.; Cui, J. L.; Mashuta, M. S.; Grapperhaus, C. A.; Buchanan, R. M. Tetrahedron Lett. 2011, 52, 4771-4774 "Metal-Stabilized Thiyl Radicals as Scaffolds for Reversible Alkene Addition via C-S Bond Formation/Cleavage" Ouch, K.; Mashuta, M. S.; Grapperhaus, C. A. Inorg. Chem. 2011, 50, 9904–9914.