Synthesis of cis- and trans-bis(phosphine)bis(thiolato)platinum(II) complexes, (PR3)2Pt(SR′)2

Article abstract of DOI:10.1021/ic50216a032

Complexes of the type L₂Pt(SR)₂ are isolated in high purity and yield by treating the cis-dichlorides with thiols under nitrogen atmosphere in the presence of triethylamine, L = PPh₃, PMePh₂, PMe₂Ph, and 1/2(PPh₂CH₂)₂, and R = CH₂Ph, i-C₃H₇, n-C₃H₇, and 4-C₆H₄CH₃. For R = alkyl the complexes have been assigned the cis geometry while for R = aryl they have been assigned the trans configuration on the basis of NMR studies. The cis-bis(thiolato) complexes tend to rearrange to a complex mixture of the trans complexes and other species upon exposure to air in solution. It is proposed that this surprising sensitivity accounts for the relative rarity of complexes of the type cis-L₂Pt(SR)₂ where L₂ or the thiolato ligands are not chelates.