New Mixed-Metal Sulfido Metal Carbonyl Complexes by Insertion of Metal Carbonyl Groups into the S−S Bond of CpMoMn(CO)5(μ-S2)

Abstract

The disulfido compound CpMoMn(CO)5(μ-S2) (1) reacted with CpCo(CO)2 to yield two products, Cp2MoMnCo(CO)5(μ3-S)2 (2) and Cp2MoMn(CO)3OCo(μ3-S)2 (3), by insertion of a CpCo group into the S−S bond of 1. Compound 2 was found to consist of an open MoMnCo cluster with one Mo−Mn bond (2.849(2) A, one Mn−Co bond (2.605(3) A, and two triply bridging sulfido ligands. Compound 3 consists of a closed triangular CoMnMo cluster with triply bridging sulfido ligands on each side of the CoMnMo plane. Compound 3 was obtained from 2 by treatment with Me3NO. Reaction of 1 with Fe2(CO)9 yielded the complex CpMoMnFe(CO)8(μ3-S)2 (4). Reaction of 1 with Ru3(CO)12 yielded the ruthenium homologue of 4, CpMoMnRu(CO)8(μ3-S)2 (5), and a minor product, CpMoRu3(CO)9(μ3-S)2(μ-H) (6), that contains no manganese. Compounds 4 and 5 are structurally similar to 2 but contain an M(CO)3 group in place of the CpCo group. Compound 6 contains a butterfly cluster of four metal atoms with two triply bridging sulfido ligands and one bridging hydri...