Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex.
The reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex 1 was intensively studied. A series of sulfur-coordinated organocobalt complexes (2-8) were obtained through the reactions of 1 with RX (RX = HCl, C2H5Br and CH3I), 2-(diphenylphosphanyl)phenol, 2-(diphenylphosphino)benzenethiol, and CO. The reaction of complex with ethynyltrimethylsilane under 1 bar of CO afforded a penta-coordinate cobalt(I) complex 11 via insertion reaction of C≡C bond of ethynyltrimethylsilane into Co-H bond and subsequent C,C-coupling reaction (reductive elimination). The formation mechanism of 11 was proposed and partly-experimentally verified. As an intermediate, the tetra-coordinate cobalt(I) complex 13 was isolated through the reaction of complex 1 with ethynyltrimethylsilane in the absence of CO. The crystal structures of complexes 2-4, 8, and 11 were determined by X-ray diffraction.
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250199 Jinan, PR China. huqingping@sdu.edu.cn xli63@sdu.edu.cn.
Qingfen
Q
Niu
Hongjian
H
Sun
Lin
L
Wang
Qingping
Q
Hu
Xiaoyan
X
Li