Synthesis, structures and redox properties of platinum metal phosphathia complexes: Crystal structures of cis-[RuCl2(RSC(2)H(4)SR)]center dot 0.75Et(2)O and cis-[RhCl2(RSC(2)H(4)RS)]PF6 center dot CH2Cl2 (R=Ph(2)PCH(2)CH(2))

Reaction of [RuCl2(py)(4)] (py = pyridine) with 1 molar equivalent of the new tetradentate acyclic phosphathia compound RSC(2)H(4)SR (Ph(2)PCH(2)CH(2)SCH(2)CH(2)SCH(2)CH(2)PPh(2)) or the macrocycle meso-Ph(2)[14]aneP(2)S(2) (4,8-diphenyl-1,11-dithia-4,18-diphosphacyclotetradecane) in refluxing toluene under a nitrogen atmosphere afforded the ruthenium(II) complexes [RuCl2(RSC(2)H(4)SR)] and [RuCl2(Ph(2)[14]aneP(2)S(2))] respectively as yellow solids; The crystal structure of [RuCl2(RSC(2)H(4)SR)]. 0.75Et(2)O shows RSC(2)H(4)SR co-ordinated via all four donor atoms with the two P-donors occupying mutually trans co-ordination sites at Ru-II, and cis-dichlorides completing the overall octahedral stereochemistry, Ru-S 2.294(1), 2.292(1), Ru-P 2.339(2), 2.335(2), Ru-C12.463(1), 2.463(1) Angstrom. Phosphorus-31 NMR spectroscopic studies on the macrocyclic species [RuCl2(Ph(2)[14]aneP(2)S(2))] are consistent with a cis-dichloro isomer in which one Cl is trans to P and the other trans to S. Cyclic voltammetry showed a reversible one-electron oxidation occurring at E(1/2) = +0.16 and +0.32 V vs. ferrocene-ferrocenium for [RuCl2(RSC(2)H(4)SR)] and [RuCl2(Ph(2)[14]aneP(2)S(2))] respectively. The complexes [MCl(2)(RSC(2)H(4)SR)]PF6 (M = Rh or Ir) have also been prepared. The structure of [RhCl2(RSC(2)H(4)SR)]PF6 . CH2Cl2 shows discrete [RhCl2(RSC(2)H(4)SR)](+) cations adopting a very similar arrangement to that in the ruthenium(II) analogue, with Rh-P 2.352(2), 2.342(2), Rh-S 2.303(2), 2.297(2), Rh-Cl 2.370(2), 2.359(2) Angstrom. Rhodium-103 NMR spectroscopy reveals a triplet at delta + 1405 (J(RhP) 85 Hz).