Reaction of [RuCl2(py)4] (py = pyridine) with 1 molar equivalent of the new tetradentate acyclic phosphathia compound RSC2H4SR (Ph2PCH2CH2SCH2CH 2SCH2CH2PPh2) or the macrocycle meso-Ph2aneP2S2 (4,8-diphenyl-1,11-dithia-4,18-diphosphacyclotetradecane) in refluxing toluene under a nitrogen atmosphere afforded the ruthenium(II) complexes [RuCl2(RSC2H4SR)] and [RuCl2(Ph2aneP2S2)] respectively as yellow solids. The crystal structure of [RuCl2(RSC2H4SR)]·0.75Et2O shows RSC2H4SR co-ordinated via all four donor atoms with the two P-donors occupying mutually trans co-ordination sites at RuII, 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-Cl2.463(1), 2.463(1) Å. Phosphorus-31 NMR spectroscopic studies on the macrocyclic species [RuCl2(Ph2aneP2S2)] 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 E1/2 = +0.16 and +0.32 V vs. ferrocene-ferrocenium for [RuCl2(RSC2H4SR)] and [RuCl2(Ph2aneP2S2)] respectively. The complexes [MCl2(RSC2H4SR)]PF6 (M = Rh or Ir) have also been prepared. The structure of [RhCl2(RSC2H4SR)]PF6·CH 2Cl2 shows discrete [RhCl2(RSC2H4SR)]+ 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) Å. Rhodium-103 NMR spectroscopy reveals a triplet at δ + 1405 (JRhP 85 Hz).
|Number of pages||6|
|Journal||Journal of the Chemical Society - Dalton Transactions|
|Publication status||Published - 7 Apr 1996|
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