The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics

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• 作者：Deven P. Estes ; David C. Grills ; Jack R. Norton
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：December 17, 2014
• 年：2014
• 卷：136
• 期：50
• 页码：17362-17365
• 全文大小：329K
• ISSN：1520-5126

文摘

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鈥搗is 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鈥揌 bond in 6a to be 50.5 kcal/mol and 13.4, respectively, in CH₃CN, matching previous reports.