Synthesis and structure of [An(RO)PS2]− complexes

Abstract

Reaction of An(S)PS₂P(S)An with NaOR [R = Me, Et, ⁱPr] gives the non-symmetric phosphonodithioato anions [An(RO)PS₂]⁻ which can be complexed to a range of metals. The group 10 metals (Ni, Pd and Pt) adopt square planar ML₂ complexes. The zinc and cadmium complexes adopt isostructural dimeric M₂L₄ structures whilst mercury complexes adopt a subtly different dimeric motif. Two distinctly different lead complexes are reported, one consisting of PbL₂ units joined by Pb⋯S interactions to form distinct dimeric pairs, the other being a completely new structural motif for complexes of this type, PbL₂ units held together by covalently bonded bridging ligands to form an infinite polymeric chain structure. All new compounds have been characterised spectroscopically and nine demonstrative X-ray structures are reported.