The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics
The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics
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DOI：
10.1021/ja508200g
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发表时间：
2014-12-17
影响因子：
15
通讯作者：
Norton, Jack R.
中科院分区：
文献类型：
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作者：
Estes, Deven P.;Grills, David C.;Norton, Jack R.
在Co(dmgBF(2))(2)L-2体系的许多反应中，钴的氢化物被认为是一个中间体，但它的观察是困难的。我们观察到了Co(dmgBF(2))(2)L-2(1)在CH3CN中氢压高达70atm时的紫外可见光谱。最终形成具有可交换质子的Co(I)化合物(6a)。我们在CH3CN中测得6a中新的O-H键的键离解能和pK(A)分别为50.5千卡/摩尔和13.4千卡/摩尔，与以前的报道一致。
A cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF(2))(2)L-2 system, but its observation has proven difficult. We have observed the UV-vis spectra of Co(dmgBF(2))(2)L-2 (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.