Synthesis and characterisation of some [M(C3S5)2]n- complexes (M = Ni, Pd, Pt). Single crystal structure of [PPN][Ni(C3S5)2] · MeOH

Article abstract of DOI:10.1016/S0277-5387(97)00131-9

The synthesis and characterisation of some anionic Ni, Pd and Pt complexes of the ligand, Na₂C₃S₅, (C₃S^2-₅ = 1,3-dithiole-2-thione-4,5-dimercapto = dmit) are reported. The complexes were isolated as PPN⁺ [PPN⁺ = bis(triphenylphosphine)iminium] salts. The monoanionic complexes [PPN] [Ni(C₃S₅)₂] and [PPN] [Pd(C₃S₅)₂] were further oxidised with iodine in acetonitrile to afford [PPN]_0.25[Ni(C₃S₅)₂] and [PPN]_0.25[Pd(C₃S₅)₂]. The partially oxidised complexes have electrical conductivities of 1.2 × 10^-2 and 0.64 S cm^-1 at room temperature for compacted pellets. Cyclic voltammetry, electronic, IR and ESR spectra of the complexes are discussed. A single crystal X-ray determination of [PPN] [Ni(C₃S₅)₂] · MeOH was carried out. The average value of Ni - S bond length is one of the highest observed for a [Ni(dmit)₂] complex.