期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 22, 页码 8527-8531出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201914718
关键词
amido cobalt complex; catalysis; C-H activation; H atom transfer; imido cobalt complex
资金
- DFG [WE 5627/4-1]
The 3d-metal mediated nitrene transfer is under intense scrutiny due to its potential as an atom economic and ecologically benign way for the directed amination of (un)functionalised C-H bonds. Here we present the isolation and characterisation of a rare, trigonal imido cobalt(III) complex, which bears a rather long cobalt-imido bond. It can cleanly cleave strong C-H bonds with a bond dissociation energy of up to 92 kcal mol(-1) in an intermolecular fashion, unprecedented for imido cobalt complexes. This resulted in the amido cobalt(II) complex [Co(hmds)(2)((NHBu)-Bu-t)](-). Kinetic studies on this reaction revealed an H atom transfer mechanism. Remarkably, the cobalt(II) amide itself is capable of mediating H atom abstraction or stepwise proton/electron transfer depending on the substrate. A cobalt-mediated catalytic application for substrate dehydrogenation using an organo azide is presented.
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