Reactions of chloro-olefins and chloroalkanes with tetrakis(triphenylphosphine)platinum(0)

Abstract

Reactions of tetrachloroethylene and tetrafluoroethylene with (Ph₃P)₄Pt give the olefin complexes (Ph₃P)₂Pt(olefin). The tetrachloroethylene complex can be isomerised to the vinyl complex (Ph₃P)₂Pt(CClCCl₂)Cl. This isomerisation is solvent-dependent. Trichloroethylene and trans-1,2-dichloroethylene with (Ph₃P)₄Pt give only the vinyls (Ph₃P)₂Pt(CHCCl₂)Cl and (Ph₃P)₂Pt(CHCHCl)Cl, while cis-1,2-dichloroethylene and hexachloropropene give cis-(Ph₃P)₂PtCl₂. Reactions of hexachloroethane and chloroform with Pt(PPh₃)₄ give cis-(Ph₃P)₂PtCl₂, and bromotrichloromethane gives cis-(Ph₃P)₂PtBr₂. Carbon tetrachloride gives a product which is probably (Ph₃P)₂Pt(CCl₃)Cl. Infrared and n.m.r. spectra of the products are reported.