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Issue 10, 2014
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Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex

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Abstract

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 1 with ethynyltrimethylsilane under 1 bar of CO afforded a penta-coordinate cobalt(I) complex 11via insertion reaction of C[triple bond, length as m-dash]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.

Graphical abstract: Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(iii) complex

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Publication details

The article was received on 13 Sep 2013, accepted on 25 Nov 2013 and first published on 28 Nov 2013


Article type: Paper
DOI: 10.1039/C3DT52519H
Citation: Dalton Trans., 2014,43, 4059-4066

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    Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex

    Q. Niu, H. Sun, L. Wang, Q. Hu and X. Li, Dalton Trans., 2014, 43, 4059
    DOI: 10.1039/C3DT52519H

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