New mixed-metal sulfido metal carbonyl complexes by insertion of metal carbonyl groups into the S-S bond of CpMoMn(CO)5(μ-S2)

The disulfido compound CpMoMn(CO)(5)(mu-S-2) (1) reacted with CpCo(CO)(2) to yield two products, Cp2MoMnCo(CO)(5)(mu(3)-S)(2) (2) and Cp2MoMn(CO)(3)OCo(mu(3)-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) Angstrom, one Mn-Co bond (2.605(3) Angstrom, 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 Fe-2(CO)(9) yielded the complex CpMoMnFe(CO)(8)(mu(3)-S)(2) (4). Reaction of 1 with Ru-3(CO)(12) yielded the ruthenium homologue of 4, CpMoMnRu(CO)(8)(mu(3)-S)(2) (5), and a minor product, CpMoRu3(CO)(9)(mu(3)-S)(2)(mu-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 hydride ligand.