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(Pr-i) and C6Me6), [RuCl2(eta(3):eta(3)-C10H16)(PS)], [RhCl(cod)(PS)] (cod = 1,5-cyclooctadiene) and [(CP*)MCl2(PS)] (Cp* = pentamethylcyclopentadienyl, M = Rh or It) (where. PS = Ph2PNHC6H4P(S)Ph-2) have been synthesised by the reaction of Ph2PNHC6H4P(S)Ph-2 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{Pr-i})RuCl(PS)][ClO4], [Rh(cod)(PS)][ClO4] and [(Cp*)RhC](PS)[ClO4] in which the ligand is k(2)-P,S bound. All new compounds were characterised by a combination of P-31{H-1} and H-1 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. (C) 2002 Elsevier Science Ltd. All rights reserved.