Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes

Anirban Bhattacharjee, Murielle Chavarot-Kerlidou, Jillian L. Dempsey, Harry B. Gray, Etsuko Fujita, James Muckerman, Marc Fontecave, Vincent Artero, Guilherme M. Arantes, Martin J. Field

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The reduced CoI 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. Hydrogen anyone? Cobaloximes are efficient hydrogen-evolving catalysts. A combined experimental and theoretical study provides insights into the electronic structures of the reduced forms of these compounds which are known to be important intermediates in their catalytic cycles.

Original languageEnglish
Pages (from-to)2951-2958
Number of pages8
JournalChemPhysChem
Volume15
Issue number14
DOIs
Publication statusPublished - Oct 1 2014

Fingerprint

Absorption spectra
Hydrogen
absorption spectra
hydrogen
electronics
Nucleophiles
nucleophiles
Molecular orbitals
Electronic structure
Density functional theory
catalytic activity
energy
Catalyst activity
molecular orbitals
density functional theory
electronic structure
catalysts
orbitals
cycles
Catalysts

Keywords

  • catalysis
  • cobaloxime complexes
  • hydrogen evolution
  • theoretical electronic spectra
  • Vitamin B mimics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Bhattacharjee, A., Chavarot-Kerlidou, M., Dempsey, J. L., Gray, H. B., Fujita, E., Muckerman, J., ... Field, M. J. (2014). Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes. ChemPhysChem, 15(14), 2951-2958. https://doi.org/10.1002/cphc.201402398

Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes. / Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

In: ChemPhysChem, Vol. 15, No. 14, 01.10.2014, p. 2951-2958.

Research output: Contribution to journalArticle

Bhattacharjee, A, Chavarot-Kerlidou, M, Dempsey, JL, Gray, HB, Fujita, E, Muckerman, J, Fontecave, M, Artero, V, Arantes, GM & Field, MJ 2014, 'Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes', ChemPhysChem, vol. 15, no. 14, pp. 2951-2958. https://doi.org/10.1002/cphc.201402398
Bhattacharjee, Anirban ; Chavarot-Kerlidou, Murielle ; Dempsey, Jillian L. ; Gray, Harry B. ; Fujita, Etsuko ; Muckerman, James ; Fontecave, Marc ; Artero, Vincent ; Arantes, Guilherme M. ; Field, Martin J. / Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes. In: ChemPhysChem. 2014 ; Vol. 15, No. 14. pp. 2951-2958.
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