Coordination chemistry of o-Ph2PNHC6H4P(S)Ph2 a P,S-donor ligand: synthesis of new Ru, Rh and Ir complexes

The late transition metal complexes [(Ar)RuCl2(PS)] (Ar=C6H6, o-MeC6H4(iPr) and C6Me6), [RuCl2(η3:η3-C10H16)(PS)], [RhCl(cod)(PS)] (cod=1,5-cyclooctadiene) and [(Cp*)MCl2(PS)] (Cp*=pentamethylcyclopentadienyl, M=Rh or Ir) (where PS=Ph2PNHC6H4P(S)Ph2) have been synthesised by the reaction of Ph2PNHC6H4P(S)Ph2 with the appropriate chloride bridged transition metal dimers. In all of these complexes the ligand is monodentate P-bound. Chloride abstraction from representative complexes, using Ag[ClO4], gave the cationic compounds [(o-MeC6H4{iPr})RuCl(PS)][ClO4], [Rh(cod)(PS)][ClO4] and [(Cp*)RhCl(PS)][ClO4] in which the ligand is k2-P,S bound. All new compounds were characterised by a combination of 31P{1H} and 1H NMR spectroscopy, microanalysis, FAB mass spectrometry and IR spectroscopy. The molecular structures of five complexes have been determined by single-crystal X-ray diffraction—both monodentate and chelate coordination has been characterised. The P-monodentate compounds all display intramolecular NH⋯S hydrogen bonding.