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

Article abstract of DOI:10.1016/S0277-5387(02)01357-8

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.