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钴卟啉与氢气的反应:产物与热力学。

The reaction of cobaloximes with hydrogen: products and thermodynamics.

机构信息

Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.

出版信息

J Am Chem Soc. 2014 Dec 17;136(50):17362-5. doi: 10.1021/ja508200g. Epub 2014 Dec 9.

DOI:10.1021/ja508200g
PMID:25427140
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.

摘要

一种钴氢化物被认为是 Co(dmgBF2)2L2 体系中许多反应的中间体,但很难观察到。我们已经在 CH3CN 中观察到了高达 70 个大气压的 Co(dmgBF2)2L2(1)的紫外可见光谱。最终形成了一种具有可交换质子的 Co(I)化合物(6a)。我们已经确定了在 CH3CN 中 6a 中新的 O-H 键的键离解自由能和 pK(a)分别为 50.5 kcal/mol 和 13.4,与之前的报道相匹配。

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