Synthesis and reactivity of a novel hydridocobalt(III) complex containing trimethylphosphine and thiophenolato ligands

The novel hydridocobalt(III) complex [mer-Co(H)(SPh)2(PMe3)3] (1) was prepared by reaction of thiophenol with [Co(PMe3)3Cl], [Co(PMe3)4] and [Co(PMe3)4Me]. A dinuclear cobalt dithiophenolato complex [Co(PMe3)2(SPh)]2 (2) was obtained from the reaction of thiophenol with [Co(PMe3)4Me]. Reaction of 1 with iodomethane afforded complex [Co(PMe3)3(I)2] (3). Reaction of complex 2 with carbon monoxide gave a mononuclear dicarbonyl cobalt(I) complex [Co(PMe3)3(CO)2(SPh)] (4). The crystal structures of 1–4 were determined by X-ray diffraction. Formation mechanism of 1 is discussed.