The reaction of cobaloximes with hydrogen: Products and thermodynamics

Deven P. Estes; David C. Grills; Jack R. Norton

doi:10.1021/ja508200g

The reaction of cobaloximes with hydrogen: Products and thermodynamics

Deven P. Estes, David C. Grills, Jack R. Norton

Brookhaven National Laboratory

Research output: Contribution to journal › Article › peer-review

70 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	17362-17365
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	50
DOIs	https://doi.org/10.1021/ja508200g
Publication status	Published - Dec 17 2014

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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AB - 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 pKa of the new O-H bond in 6a to be 50.5 kcal/mol and 13.4, respectively, in CH3CN, matching previous reports.

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The reaction of cobaloximes with hydrogen: Products and thermodynamics

Abstract

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