Synthesis and late transition metal complexes of the heterofunctional phosphane o-Ph₂PNHC₆H₄P(S)Ph₂

The difunctional ligand o-Ph2PNHC6H4P(S)Ph-2 (PS) has been prepared by treatment of the lithium amide salt of 2-(diphenylthiophosphanyl) aniline {2-[Ph2P(S)]C6H4NH2} with Ph2PCl. The new ligand was oxidised to give the mixed chalcogen species Ph2P(E)NHC6H4P(S)Ph-2, by treatment with H2O2 (where E = O) or aerial oxidation by recrystallisation from MeOH, and by reaction with Se-8 (where E = Se) in warm toluene. The complexes [MCl(eta(3)-C3H5)(PS)] (M = Pt or Pd), CiS-[PtCl2(PS)(PMe2Ph)], [(AuCl)(PS)], CiS-[MCl2(PS)(2)] (M = Pt or Pd), cis-[PtMe2(PS)(2)] and trans-[PtMeCl(PS)(2)] have been synthesised by reaction of either [Pt(mu-Cl)(mu-eta(2):eta(1)-C3H5)](4), [Pd(mu-Cl)(eta(3)-C3H5)](2), [{PtCl(mu-Cl)(PMe2Ph)}(2)], [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(cod)] or [PtX2(cod)] (X = Me or Cl; cod = cycloocta-1,5-diene) with (PS). In all these complexes the ligand (PS) is monodentate P-bound. Chloride abstraction from [MCl(eta(3)-C3H5)(PS)] (M = Pt or Pd), CiS-[PtCl2(PS)(PMe2Ph)], cis-[PtCl2(PS)(2)] and trans[PtMeCl(PS)(2)], using Ag[ClO4], gave the monocationic [M(eta(3)-C3H5)(PS)][ClO4] (M = Pt or Pd), cis-[PtCl(PS)(PMe2Ph)][ClO4], trans-[PtMe(PS)(2)] [ClO4] or dicationic [Pt(PS)(2)][ClO4](2) compounds in which the ligand (PS) is kappa(2)-P, S-bound. All compounds described here have been characterised by a combination of P-31{H-1} and H-1 NMR spectroscopy, microanalyses, FAB mass spectrometry and IR spectroscopy. The molecular structures of [AuCl(Ph2PNHC6H4P-(S)Ph-2-P)] in which there is an intramolecular hydrogen-onding interaction between the amine proton and the sulfur atom of the thiophosphoryl group and transt-[Pt(Ph2PNHC6H4P(S)Ph-2-kappa(2)-P,S)(2)][ClO4](2).CH2Cl2.2H(2)O in which the perchlorate counterions are associated by hydrogen-bonding interactions to the amine protons of the kappa(2)-P,S ligands have been determined by single-crystal X-ray diffraction.