α-选择性钴催化炔烃硼氢化反应中的反应途径和氧化还原状态

Blasius Clemens K, Vasilenko Vladislav, Matveeva Regina, Wadepohl Hubert, Gade Lutz H

Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23010-23014. doi: 10.1002/anie.202009625. Epub 2020 Oct 15.

Cobalt(II) alkyl complexes supported by a monoanionic NNN pincer ligand are pre-catalysts for the regioselective hydroboration of terminal alkynes, yielding the Markovnikov products with α:β-(E) ratios of up to 97:3. A cobalt(II) hydride and a cobalt(II) vinyl complex appear to determine the main reaction pathway. In a background reaction the highly reactive hydrido species specifically converts to a coordinatively unsaturated cobalt(I) complex which was found to re-enter the main catalytic cycle.

由单阴离子NNN钳形配体支持的钴（II）烷基配合物是末端炔烃区域选择性硼氢化反应的预催化剂，生成的马氏产物的α:β-（E）比例高达97:3。一种氢化钴（II）和一种乙烯基钴（II）配合物似乎决定了主要反应途径。在一个背景反应中，高活性的氢化物物种特异性地转化为一种配位不饱和的钴（I）配合物，发现该配合物会重新进入主要催化循环。