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Title: Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

Abstract

Here, we report that 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 have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using 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:
 [1];  [1];  [2];  [3];  [4];  [4];  [5];  [1];  [6];  [1]
  1. Univ. of Grenoble, Grenoble Cedex (France)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States); Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
  3. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Univ. of Grenoble, Grenoble Cedex (France); College de France, Paris (France)
  6. Univ. de Sao Paulo, Sao Paulo (Brazil)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1281077
Grant/Contract Number:  
AC02-98CH10886; CHE-1305124; 306398
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 15; Journal Issue: 14; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cobaloxime complexes; H2 evolving catalysts; theoretical electronic spectra; vitamin B12 mimics

Citation Formats

Bhattacharjee, Anirban, Chavarot-Kerlidou, Murielle, Dempsey, Jillian L., Gray, Harry B., Fujita, Etsuko, Muckerman, James T., Fontecave, Marc, Artero, Vincent, Arantes, Guilherme M., and Field, Martin J. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes. United States: N. p., 2014. Web. doi:10.1002/cphc.201402398.
Bhattacharjee, Anirban, Chavarot-Kerlidou, Murielle, Dempsey, Jillian L., Gray, Harry B., Fujita, Etsuko, Muckerman, James T., Fontecave, Marc, Artero, Vincent, Arantes, Guilherme M., & Field, Martin J. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes. United States. doi:10.1002/cphc.201402398.
Bhattacharjee, Anirban, Chavarot-Kerlidou, Murielle, Dempsey, Jillian L., Gray, Harry B., Fujita, Etsuko, Muckerman, James T., Fontecave, Marc, Artero, Vincent, Arantes, Guilherme M., and Field, Martin J. Mon . "Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes". United States. doi:10.1002/cphc.201402398. https://www.osti.gov/servlets/purl/1281077.
@article{osti_1281077,
title = {Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes},
author = {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.},
abstractNote = {Here, we report that 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 have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using 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.},
doi = {10.1002/cphc.201402398},
journal = {ChemPhysChem},
number = 14,
volume = 15,
place = {United States},
year = {Mon Aug 11 00:00:00 EDT 2014},
month = {Mon Aug 11 00:00:00 EDT 2014}
}

Journal Article:
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Cited by: 7 works
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