The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics

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 of up to 70 atm. A Co­(I) compound (6a) with an exchangeable pro...

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Published inJournal of the American Chemical Society Vol. 136; no. 50; pp. 17362 - 17365
Main Authors Estes, Deven P, Grills, David C, Norton, Jack R
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 17.12.2014
American Chemical Society (ACS)
Subjects
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary: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 of up to 70 atm. A Co­(I) compound (6a) with an exchangeable proton is eventually formed. We have determined the bond dissociation free energy and pK a of the new O–H bond in 6a to be 50.5 kcal/mol and 13.4, respectively, in CH3CN, matching previous reports.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
BNL-107850-2015-JA
USDOE Office of Science (SC), Basic Energy Sciences (BES)
SC00112704
ISSN:0002-7863
1520-5126
DOI:10.1021/ja508200g