Synthesis and Late Transition Metal Complexes of the Heterofunctional Phosphane o ‐Ph 2 PNHC 6 H 4 P(S)Ph 2

The difunctional ligand o ‐Ph 2 PNHC 6 H 4 P(S)Ph 2 (PS) has been prepared by treatment of the lithium amide salt of 2‐(diphenylthiophosphanyl)aniline {2‐[Ph 2 P(S)]C 6 H 4 NH 2 } with Ph 2 PCl. The new ligand was oxidised to give the mixed chalcogen species Ph 2 P(E)NHC 6 H 4 P(S)Ph 2 , by treatment with H 2 O 2 (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(η 3 ‐C 3 H 5 )(PS)] (M = Pt or Pd), cis ‐[PtCl 2 (PS)(PMe 2 Ph)], [(AuCl)(PS)], cis ‐[MCl 2 (PS) 2 ] (M = Pt or Pd), cis ‐[PtMe 2 (PS) 2 ] and trans ‐[PtMeCl(PS) 2 ] have been synthesised by reaction of either [Pt(μ‐Cl)(μ‐η 2 :η 1 ‐C 3 H 5 )] 4 , [Pd(μ‐Cl)(η 3 ‐C 3 H 5 )] 2 , [{PtCl(μ‐Cl)(PMe 2 Ph)} 2 ], [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl 2 (cod)] or [PtX 2 (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(η 3 ‐C 3 H 5 )(PS)] (M = Pt or Pd), cis ‐[PtCl 2 (PS)(PMe 2 Ph)], cis ‐[PtCl 2 (PS) 2 ] and trans ‐[PtMeCl(PS) 2 ], using Ag[ClO 4 ], gave the monocationic [M(η 3 ‐C 3 H 5 )(PS)][ClO 4 ] (M = Pt or Pd), cis ‐[PtCl(PS)(PMe 2 Ph)][ClO 4 ], trans ‐[PtMe(PS) 2 ][ClO 4 ] or dicationic [Pt(PS) 2 ][ClO 4 ] 2 compounds in which the ligand (PS) is κ 2 ‐ P , S ‐bound. All compounds described here have been characterised by a combination of 31 P{ 1 H} and 1 H NMR spectroscopy, microanalyses, FAB mass spectrometry and IR spectroscopy. The molecular structures of [AuCl(Ph 2 PNHC 6 H 4 P(S)Ph 2 ‐ P )] in which there is an intramolecular hydrogen‐bonding interaction between the amine proton and the sulfur atom of the thiophosphoryl group and trans ‐[Pt(Ph 2 PNHC 6 H 4 P(S)Ph 2 ‐κ 2 ‐ P , S ) 2 ][ClO 4 ] 2 ·CH 2 Cl 2 ·2H 2 O in which the perchlorate counterions are associated by hydrogen‐bonding interactions to the amine protons of the κ 2 ‐ P , S ligands have been determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)