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Reaction of [Mn 2 (CO) 10 ] with 2-mercapto-1-methylimidazole in the presence of Me 3 NO at 25°C afforded two new dimanganese complexes [Mn 2 (CO) 6 (μ-SN 2 C 4 H 5 ) 2 ] (1) and [Mn 2 (CO) 7 (μ-SN 2 C 4 H 5 ) 2 ] (2). Compound 1 consists of two μ-SN 2 C 4 H 5 ligands, each bound through the sulfur atom to two Mn atoms and through the nitrogen atom to one Mn atom forming a four-membered chelate ring. Compound 2 was found to consist of one μ-SN 2 C 4 H 5 ligand in a similar bonding mode to 1 but another μ-SN 2 C 4 H 5 ligand coordinates through the sulfur atom to one Mn atom and through the nitrogen atom to another Mn atom. Compound 1 was also obtained as the only product from the reaction of [Mn 2 (CO) 8 (NCMe) 2 ] with 2-mercapto-1-methylimidazole. In contrast, a similar reaction of [Re 2 (CO) 8 (NCMe) 2 ] with 2-mercapto-1-methylimidazole led to the formation of the di-, tri-, and tetranuclear complexes [Re 3 (CO) 8 (μ-CO)(μ 3 -SN 2 C 4 H 5 ) 2 (μ-H)] (3), [Re 4 (CO) 12 (μ-SN 2 C 4 H 5 ) 4 ] (4), and [Re 2 (CO) 6 (μ-SN 2 C 4 H 5 ) 2 ] (5). Compound 3 provides a unique example of a hydrido trirhenium compound. The reaction of [Cr(CO) 3 (NCMe) 3 ] and

Reactions of the dirhenium and dimanganese complexes [Re2(CO)10−x(NCMe)x] (x = 0, 1, 2) and [Mn2(CO)10] with tri(2-thienyl)phosphine in different conditions are studied. A variety of mono-and dinuclear complexes are obtained from these reactions by C-P bond cleavage of the tri(2thienyl)phosphine ligand.

Triruthenium carbonyls react with 2-vinylpyridene, leading to a previously unknown double carbon−hydrogen bond activation of the β-carbon of the vinyl group to afford a dimetalated 2-vinylpyridyl ligand which can adopt different coordination modes.

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