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

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.
 [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:
Grant/Contract Number:
AC02-98CH10886; CHE-1305124; 306398
Accepted Manuscript
Journal Name:
Additional Journal Information:
Journal Volume: 15; Journal Issue: 14; Journal ID: ISSN 1439-4235
ChemPubSoc Europe
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE; National Science Foundation (NSF)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cobaloxime complexes; H2 evolving catalysts; theoretical electronic spectra; vitamin B12 mimics
OSTI Identifier: