Metal halide complexes of triphenylphosphine sulphide and some related ligands

Abstract

Triphenylphosphine sulphide forms stable complexes with halides of Pd^II, Pt^II, Pt^IV, Au^III, Au^I, and Hg^II. Triphenylphosphine selenide and triphenylarsine sulphide are generally similar but decompose with Au^III and Pt^IV, and triphenylstibine sulphide gives identifiable adducts only with copper(I) iodide and mercury(II) iodide. Ph₃AsS extracts Pt^II from aqueous solution approximately seven times as fast as Ph₃PSe, and sixteen times as fast as Ph₃PS. The 1 : 1 adducts of HgCl₂ with Ph₃PS, Ph₃PSe, and Ph₃AsS are isomorphous with one another but not with dimeric (HgCl₂,Ph₃AsO)₂. The P–S stretching frequency in Ph₃PS falls by 40–50 cm.^–1 on co-ordination, and the P–Se stretching frequency in Ph₃PSe by about 20 cm.^–1.