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The international journal for inorganic, organometallic and bioinorganic chemistry



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Paper

J. Chem. Soc., Dalton Trans., 1996, 1093 - 1104, DOI: 10.1039/DT9960001093

Complexes of potentially tri- and tetra-dentate phosphinothiol ligands with Mo, W, Re, Fe, Ru, Os, Rh, Ir and Ni

Jonathan R. Dilworth, Anthony J. Hutson, Jason S. Lewis, John R. Miller, Yifan Zheng, Qin Chen and Jon Zubieta

The phosphinothiolate proligand PPh(C6H4SH-2)2(H2L2) reacted with a variety of precursors to give the complexes [ML22]n–(M = Mo, W or Re, n= 0; M = Fe, Ru, Os, Rh or Ir, n= 1). The crystal structure of the complex with M = Re revealed a distorted-octahedral geometry with the L2 ligands facially co-ordinated. Other precursors gave the complexes [ML22X]n–(X = Cl, M = Re, n= 0; X = NO, M = Mo, n= 1; M = Ru, n= 0; X = NR, M = Re, n= 1; X = NNMePh, M = Mo, n= 0; M = Ru, n= 1). The geometry of these seven-co-ordinate complexes is discussed. The metal(0) complexes [M(CO)3(MeCN)3](M = Mo or W) reacted with [NMe4]2[L2] to give orange [NMe4]2[ML2(CO)3] the crystal structure of which (M = Mo) showed near-octahedral geometry with facially co-ordinated L2. The complex [IrCl(CO)(PPh3)2] reacted with H2L2 to give the iridium(III) hydride [IrL2(H)(CO)(PPh3)]. Its crystal structure showed the expected octahedral geometry with the H atom presumed to be trans to a thiolate sulfur. The potentially tetradentate ligand P(C6H4SH-2)3(H3L3) reacted with precursors containing Ru, Os and Rh to give [M(HL3)2]–(M = Ru, Os or Rh) where each HL3 ligand is ligated via P and 2S with one unco-ordinated thiol group. These complexes were oxidised in air to give [M(L32)]n+(M = Ru or Os, n= 0; M = Rh, n= 1) where L32 is a hexadentate ligand formed by the coupling of two L3 through two disulfide bonds.