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

Bhattacharjee, Anirban and Chavarot-Kerlidou, Murielle and Dempsey, Jillian L. and Gray, Harry B. and Fujita, Etsuko and Muckerman, James T. and Fontecave, Marc and Artero, Vincent and Arantes, Guilherme M. and Field, Martin J. (2014) Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes. ChemPhysChem, 15 (14). pp. 2951-2958. ISSN 1439-4235. PMCID PMC4530012.

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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.

Item Type:Article
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URLURL TypeDescription CentralArticle
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Article first published online: 11 Aug 2014. Manuscript Revised: 8 Jul 2014. Manuscript Received: 4 Jun 2014. Financial support from the French National Research Agency (NiFe-Cat, ANR-10-BLAN-7-11 and LABEX ARCANE, ANR-11-LABX- 0D03-01), the FP7 CEA-Eurotalent COFUND Programme, the CEA’s DSV-ENERGIE 2011 Programme, the European Research Council under the European Union’s Seventh Framework Programme (FP/ 2007-2013)/ERC Grant Agreement no. 306398, the NSF Center for Chemical Innovation (CCI Solar, CHE-1305124), the U.S. Department of Energy (DOE) under contract number DE-AC02- 98CH10886, and the Brazilian FAPESP (project 12/02501-4) is gratefully acknowledged.
Funding AgencyGrant Number
Agence Nationale de la Recherche (ANR)ANR-10-BLAN-7-11
Agence Nationale de la Recherche (ANR)ANR-11-LABX- 0D03-01
European Research Council (ERC)306398
Department of Energy (DOE)DE-AC02-98CH10886
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)12/02501-4
Subject Keywords: catalysis; cobaloxime complexes; hydrogen evolution; theoretical electronic spectra; vitamin B_(12) mimics
Issue or Number:14
PubMed Central ID:PMC4530012
Record Number:CaltechAUTHORS:20141111-082813986
Persistent URL:
Official Citation:Bhattacharjee, A., Chavarot-Kerlidou, M., Dempsey, J. L., Gray, H. B., Fujita, E., Muckerman, J. T., Fontecave, M., Artero, V., Arantes, G. M. and Field, M. J. (2014), Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes. ChemPhysChem, 15: 2951–2958. doi: 10.1002/cphc.201402398
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:51546
Deposited By: Ruth Sustaita
Deposited On:11 Nov 2014 20:45
Last Modified:22 Nov 2019 09:58

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