Synthesis, structures and spectroscopic properties of cyclometalated tri-tert-butylphosphine complexes of platinum(II)

Reactions of [Pt2(μ-Cl)2(C∩P)2] (C∩P = CH2C(Me2)PBut2-C,P) with various anionic ligands differing in ligand bite and denticity have been investigated and the resulting products have been characterized by elemental analyses and NMR (1H, 13C, 31P, 195Pt) spectroscopy. Stereochemistry of the complexes has been deduced by NMR spectroscopy. Structures of [Pt2(μ-SPh)2(C∩P)2], [Pt2(μ-pz)2(C∩P)2], [PtCl(Spy)(PBut3)], [Pt2(μ-SCOPh)2(C∩P)2] and [Pt{S2P(OPri)2}(C∩P)] have been established by single crystal X-ray diffraction analyses. The complex [Pt2(μ-SPh)2(C∩P)2] adopts a sym cis configuration while other binuclear complexes exist in a sym trans configuration. The molecular structure of [Pt{S2P(OPri)2}(C∩P)] revealed that complex comprises of two four-membered chelate rings but in solution a dimeric structure based on 195Pt NMR data has been suggested.