Sulphur-ligand–metal complexes. Part 8. Bis(diphenylphosphinothioyl)methane complexes of copper(I)

Abstract

Crystals of [(CuClL²)₂2(CuClL²)][L²= bis(diphenylphosphinothioyl)methane] are triclinic, space group P, with a= 11.345(2), b= 16.569(3), c= 14.512(2)Å, α= 81.05(1), β= 78.76(1), γ= 109.09(1)°, and Z= 2. The structure was solved by direct methods and refined to R= 0.098 full-matrix least squares for 4 267 diffractometer data. It shows [(CuClL²)₂2(CuClL²)] to be structurally mixed complex with three-co-ordinate monomers tetrahedral sulphur-bridged dimers, co-existing in the same crystal. The formation of [(CuClL²)₂2(CuClL²)] from [CuClL²]. Me₂CO (a three-co-ordinate monomer) has been followed by differential scanning calorimetry. The interaction of L², PMe₂PhS, and P(NEt₂)₃S with copper(II) ions has allowed the identification of Ph₂P(S) CH₂P(O)Ph₂, PMe₂PhO, and [(Et₂N)₃ P–S–S–P(NEt₂)₃]²⁺ respectively, as oxidised ligand species.