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

Abstract

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:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1183829
Report Number(s):
BNL-107850-2015-JA
Journal ID: ISSN 0002-7863; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource 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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Estes, Deven P., Grills, David C., and Norton, Jack R. The reaction of cobaloximes with hydrogen: Products and thermodynamics. United States: N. p., 2014. Web. doi:10.1021/ja508200g.
Estes, Deven P., Grills, David C., & Norton, Jack R. The reaction of cobaloximes with hydrogen: Products and thermodynamics. United States. doi:10.1021/ja508200g.
Estes, Deven P., Grills, David C., and Norton, Jack R. Wed . "The reaction of cobaloximes with hydrogen: Products and thermodynamics". United States. doi:10.1021/ja508200g. https://www.osti.gov/servlets/purl/1183829.
@article{osti_1183829,
title = {The reaction of cobaloximes with hydrogen: Products and thermodynamics},
author = {Estes, Deven P. and Grills, David C. and Norton, Jack R.},
abstractNote = {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.},
doi = {10.1021/ja508200g},
journal = {Journal of the American Chemical Society},
number = 50,
volume = 136,
place = {United States},
year = {2014},
month = {11}
}

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