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.
