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

Journal Article · · ChemPhysChem
 [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)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
Grant/Contract Number:
AC02-98CH10886; CHE-1305124; 306398
OSTI ID:
1281077
Journal Information:
ChemPhysChem, Vol. 15, Issue 14; ISSN 1439-4235
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

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Cited By (3)

Structural and electronic characterization of multi-electron reduced naphthalene (BIAN) cobaloximes journal January 2015
Supramolecular assembly of cobaloxime on nanoring-coated carbon nanotubes: addressing the stability of the pyridine–cobalt linkage under hydrogen evolution turnover conditions journal January 2016
Molecular engineered nanomaterials for catalytic hydrogen evolution and oxidation journal January 2016

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cobaloxime complexes
H2 evolving catalysts
theoretical electronic spectra
vitamin B12 mimics