Synthesis of Dinuclear Cobalt Complexes Containing Trimethylphosphine and Thiophenolato Ligands

Benzene‐1,2‐dithiol reacted with Co(PMe 3 ) 4 or Co(PMe 3 ) 4 Me to afford a dinuclear complex Co 2 [C 6 H 4 (SS)] 2 (PMe 3 ) 4 ( 1 ). The cobalt complex Co 2 [C 6 H 4 (NH)S] 2 (PMe 3 ) 4 ( 2 ) was obtained from the reaction of 2‐aminothiolphenol with Co(PMe 3 ) 4 Me. From Co(PMe 3 ) 3 (CO)Cl and the lithium salt of 2‐aminothiolphenol or benzene‐1,2‐dithiol dinuclear complexes Co 2 [C 6 H 4 (NH)S](CO) 2 (PMe 3 ) 4 ( 3 ) or Co 2 [C 6 H 4 (SS)](CO) 2 (PMe 3 ) 4 ( 4 ) were obtained. The molecular structures of 1 and 4 show longer metal–metal distances [Co–Co: 2.6333(6) ( 1 ) and 2.5547(12) Å ( 4 )] than those of 2 and 3 [Co–Co: 2.4720(5) ( 2 ) and 2.457(4) Å ( 3 )]. The possible reaction mechanisms of these reactions are proposed.