期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 22, 页码 8645-8653出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201916406
关键词
carbonyls; Cu hydride; Cu-H hydride transfer; Cu-H monomerization; Cu-hemiaminalate
资金
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
- Center for Molecular Electrocatalysis, an Energy Frontier Research Center - the U.S. Department of Energy (U.S. DOE), Office of Science, Office of Basic Energy Sciences
We report mechanistic studies on the insertion reactions of [(NHC)Cu(mu-H)](2) complexes with carbonyl substrates by UV-vis and H-1 NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates, and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester or amide into the Cu-H bond.
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