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A Two-Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis, Structure, and Reactivity
Jingzhen Du1, Linbo Wang1,2, Meihua Xie2
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 (P.R. China) http://dengliang.sioc.ac.cn/
Abstract:
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(η(2) -vtms)2 ] (vtms=vinyltrimethylsilane) with DmpN3 . An X-ray diffraction study revealed its linear C-Co-N core and a short Co-N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high-spin nature of 4 and the multiple-bond 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) σ-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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