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A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis, Structure, and Reactivity

2015; Wiley; Volume: 127; Issue: 43 Linguagem: Inglês

10.1002/ange.201505937

1521-3757

Jingzhen Du, Linbo Wang, Meihua Xie, Liang Deng,

Synthetic Organic Chemistry Methods

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 DmpN 3 . 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.