个人简介

Distinguished Professor of Chemistry. B. S., 1963, Union College Kentucky. Ph. D., 1967, University of Illinois at Urbana. Inorganic Chemistry. Synthetic and mechanistic inorganic chemistry, including functioning models of catalytic active sites in bioinorganic/organometallic systems: Ni, Fe, Co.

研究领域

Bioinorganic Chemistry/Synthesis

The ultimate, home-run, goal of our work is to synthesize and develop a robust, highly active hydrogen-producing catalyst comprised of earth-abundant transition metals within a ligand environment that is inspired by the biological hydrogenase (H2ase) enzyme active sites. Progress in precise structural modeling of the illusive “rotated” structure displayed in the as-isolated, mixed-valent FeIIFeI state in the past decade has permitted in depth analysis of electronic structure by Mössbauer, EPR (ENDOR), and computational chemistry. We can conclude why this unique organometallic structure, first spotted in biology (but now achieved by distinct but convergent synthetic strategies in three laboratories) is stable! The square pyramid-inverted square pyramid structures result from sufficient disruption of Fe—Fe bond order in the FeIFeI precursors that permits steric factors to dominate and enforce rotation of one square pyramid relative to the other.

近期论文

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Hsieh, C.-H.; Ding, S.; Erdem, Ö. F.; Crouthers, D. J.; Lubitz, W.; Popescu, C. V.; Reibenspies, J. H.; Hall, M. B.; Darensbourg, M. Y. "Redox active iron nitrosyl units in proton reduction electrocatalysis." Nature Communications, 2014, 5, Article number 3684. Hsieh, C.-H.; Erdem, Ö. F.; Harman, S. D.; Singleton, M. L.; Reijerse, E.; Lubitz, W.; Popescu, C. V.; Reibenspies, J. H.; Brothers, S. M.; Hall, M. B.; Darensbourg, M. Y. "Structural and Spectroscopic Features of Mixed Valent FeIIFeI Complexes and Factors Related to the Rotated Configuration of Diiron Hydrogenase" J. Am. Chem. Soc. 2012, 134, 13089-13102. Darensbourg, M. Y.; Lyon, E. J.; Zhao, X.; Georgakaki, I. P. "The Organometallic Active Site of [Fe]Hydrogenase: Models and Entatic States" Proc. Natl. Acad. Sci. 2003, 100, 3683-3688. Singleton, M. L.; Reibenspies, J. H.; Darensbourg, M. Y. "A Cyclodextrin Host/Guest Approach to a Hydrogenase Active Site Biomimetic Cavity" J. Am. Chem. Soc., 2010, 132, 8870-8871. Hsieh, C.-H.; Darensbourg, M. Y. "A {Fe(NO)3}10 Trinitrosyliron Complex Stabilized by an N-Heterocyclic Carbene and the Cationic and Neutral {Fe(NO)2}9/10 Products of Its NO Release" J. Am. Chem. Soc., 2010, 132, 14118-14125. Hess, J. L.; Hsieh, C.-H.; Brothers, S. M.; Hall, M. B.; Darensbourg, M. Y. "Self-Assembly of Dinitrosyl Iron Units into Imidazolate-Edge-Bridged Molecular Squares: Characterization Including Mossbauer Spectroscopy" J. Am. Chem. Soc. 2011, 133, 20426-20434. Liu, T.; Li, B.; Popescu, C. V.; Bilko, A.; Pérez, L. M.; Hall, M. B.; Darensbourg, M. Y. "Analysis of a Pentacoordinate Iron Dicarbonyl as Synthetic Analogue of the Hmd or Mono-Iron Hydrogenase Active Site" Chem.- A Eur. Journal 2010, 16, 3083-3089. Hsieh, C.-H.; Chupik, R. B.; Brothers, S. M.; Hall, M. B.; Darensbourg, M. Y. "cis-Dithiolatonickel as Metalloligand to Dinitrosyl Iron Units: the Di-Metallic Structure of Ni(m-SR)[Fe(NO)2] and an Unexpected, Abbreviated Metalloadamantyl Cluster, Ni2(m-SR)4[Fe(NO)2]3" Dalton Trans. 2011, 40, 6047-6053. Li, B.; Liu, T.; Bilko, A.; Popescu, C. V.; Darensbourg, M. Y. "Synthesis and Mössbauer Characterization of Octahedral Iron(II) Carbonyl Complexes FeI(CO)3L and FeI2(CO)2L2: Developing Models of the [Fe]-H2ase Active Site" Inorganic Chemistry 2009, 48, 11283-11289. Pulukkody, R.; Kyran, S. J.; Drummond, M. J.; Hsieh, C.-H.; Darensbourg, D. J.; Darensbourg, M. Y. "Hammett correlations as test of mechanism of CO-induced disulfide elimination from dinitrosyl iron complexes.", Chem. Sci. 2014, 3795-3802