Phosphite and phosphonate complexes. Part I. Synthesis and structures of dialkyl and diphenyl phosphonate complexes of palladium and platinum

Abstract

Reactions of chloro-complexes of palladium and platinum with dialkyl and diphenyl phosphonates and their sodium and silver salts give complexes of types [(I)–(VI)]; [M{(RO)₂PO}₂{(RO)₂POH}₂](I)(M = Pd and Pt), trans-[Pt{(RO)₂PO}₂L₂](II)(L = Et₃As, Et₃P, and C₅H₅N), [MCl{(RO)₂PO}{(RO)₂POH}L](III), trans-[PtCl{(RO)₂PO}L₂](IV)(L = R₃P and Et₃As), [Pt{(RO)₂PO}₂(diphos)](V), [PdCl{(PhO)₂PO}{(PhO₂POH}](VI)(probably dimeric). The complex (IV)(R = Ph; L = Et₃As) was also obtained by heating cis-[PtCl₂–(Et₃As)₂] with [(I); M = Pt; R = Ph], and the complex [(III); M = Pt, R = Me; L = Et₃P] was obtained from (VI) and triphenylphosphine. Reaction of [(I); M = Pt; R = Ph or Me] with 1,2-bisdiphenylphosphinoethane also gave [(V); R = Ph or Me]. Metathetical reactions with complex [(III); M = Pt; R = Ph; L = Bu₃P] with sodium or silver salts of X gave the complexes [PtX{(PhO)₂PO}(Bu₃P)₂](X = Br, I, NO₂, NCO, N₃, NCS, CN, NO₃, and AcO) and the modes of co-ordination of the anionic ligands have been established. Structures have been derived from ¹H and ³¹P n.m.r. and from i.r. spectra.