title: Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes.
abstract: The reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we analyze the low-energy electronic absorption bands of two cobaloxime systems experimentally and use a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.
authors.affiliation: Dynamo Team, DYNAMOP Group, Institut de Biologie Structurale-Jean-Pierre Ebel, UMR 5075, Université Grenoble 1, CNRS, CEA, 71 Avenue des Martyrs, CS 10090, 38044 Grenoble Cedex 9 (France).
authors.forename: Anirban
authors.initials: A
authors.lastname: Bhattacharjee
authors.forename: Murielle
authors.initials: M
authors.lastname: Chavarot-Kerlidou
authors.forename: Jillian L
authors.initials: JL
authors.lastname: Dempsey
authors.forename: Harry B
authors.initials: HB
authors.lastname: Gray
authors.forename: Etsuko
authors.initials: E
authors.lastname: Fujita
authors.forename: James T
authors.initials: JT
authors.lastname: Muckerman
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
authors.forename: Vincent
authors.initials: V
authors.lastname: Artero
authors.forename: Guilherme M
authors.initials: GM
authors.lastname: Arantes
authors.forename: Martin J
authors.initials: MJ
authors.lastname: Field
mesh_terms: D008962:Models, Theoretical; D009942:Organometallic Compounds / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet / Q000379:methods
chemical_list: D009942:Organometallic Compounds; C556179:cobaloxime
keywords: catalysis; cobaloxime complexes; hydrogen evolution; theoretical electronic spectra; vitamin B12 mimics
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