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Title: The reaction of cobaloximes with hydrogen: Products and thermodynamics

In this study, a cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF₂)₂L₂ system, but its observation has proven difficult. We have observed the UV–vis spectra of Co(dmgBF₂)₂L₂ (1) in CH₃CN under hydrogen pressures up to 70 atm. A Co(I) compound (6), with an exchangeable proton, is eventually formed. We have determined the bond dissociation free energy and pKa of the new O–H bond in 6 to be 50.5 kcal/mol and 13.4, respectively, in CH₃CN, matching previous reports.
Authors:
 [1] ;  [2] ;  [1]
  1. Columbia Univ., New York, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
OSTI Identifier:
1183829
Report Number(s):
BNL--107850-2015-JA
Journal ID: ISSN 0002-7863; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 136; Journal Issue: 50; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY