期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 43, 页码 12640-12644出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201505937
关键词
carbene ligands; cobalt; multiple bonds; N ligands; structure elucidation
资金
- National Basic Research Program of China [2011CB808705]
- National Natural Science Foundation of China [21222208, 21421091, 21432001]
The synthesis, structural characterization, and reactivity of the first two-coordinate cobalt complex featuring a metal-element multiple bond [(IPr)Co(NDmp)] (4; IPr=1,3-bis(2',6'-diisopropylphenyl)imidazole-2-ylidene; Dmp=2,6-dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(eta(2)-vtms)(2)] (vtms=vinyltrimethylsilane) with DmpN(3). An X-ray diffraction study revealed its linear C-Co-N core and a short Co-N distance (1.691(6) angstrom). Spectroscopic characterization and calculation studies indicated the high-spin nature of 4 and the multiplebond character of the Co-N bond. Complex 4 effected group-transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E-H (E=C, Si) sigma-bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2-addition products.
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