Synthesis and structural characterization of [PtCl2{meso-Ph(HO)PCH2CH2P(OH)Ph}] and structurally related derivatives

The compound meso-PhH(O)PCH2CH2P(O)HPh reacted with [PtCl2(cod)] (cod = cycloocta-1,5-diene) and 2NaOMe to give the tetramer complex [{Pt[(R,S)-Ph(O)PCH2CH2P(O)Ph]}(4)]. Treatment of the latter with HCl gave [PtCl2{(R,S)-Ph(HO)PCH2CH2P(OH)Ph}] in high yield. This complex with PPh(3) gave [PtCl(PPh(3)){(R,S)-Ph(HO)PCH2CH2P(OH)Ph}]Cl which can be readily deprotonated to [PtCl(PPh(3)){(R,S)-Ph(O)PCH2CH2P(OH)Ph}] which exists in solution in two isomeric forms [P(OH)Ph group cis or trans to Cl]. Treatment of trans-[PtCl(COR)(PPh(3))(2)] (R = Me or Ph) with meso-PhH(O)PCH2CH2P(O)HPh gave the cationic complexes [Pt(COR)(PPh(3)){(R,S)-Ph(HO)PCH2CH2P(OH)Ph}]Cl (R = Me or Ph). These complexes are moisture sensitive and react readily with water. The molecular structures of three complexes have been determined by single-crystal X-ray diffraction.