Reactions of low-valent metal complexes with fluorocarbons. Part X. Reactions of tetrakis(methyldiphenylphosphine)platinum

Abstract

Tetrakis(methyldiphenylphosphine)platinum reacts with bromotrifluoroethylene to give (Ph₂PMe)₂Pt(C₂F₃Br)(I) and, unexpectedly, trans-(Ph₂PMe)₂Pt(Ph)Br (II). The fluoro-olefin complex (I) readily rearranges to the perfluorovinyl compound trans-(Ph₂PMe)₂Pt(CF:CF₂)Br (III). The rearrangement is accelerated by silver salts, and treatment of (I) or (Ph₃P)₂Pt(C₂F₃Br) with silver acetate affords respectively trans-L₂Pt(CF:CF₂)OAc (L = Ph₂PMe or Ph₃P). Treatment of (I) with carbon monoxide leads to isomerisation with formation of (Ph₂PMe)(PhPMeC₆H₄)Pt(CF:CF₂)(H) Br (IV). Reaction between (Ph₂PMe)₄Pt and C₃F₇l gives trans-(Ph₂PMe)Pt(C₃F₇)l and (Ph₂PMe)₂Pt(C₆H₅)₂l₂. The corresponding reaction with CF₃l affords trans-(Ph₂PMe)₂Pt(CF₃)l. The acid chloride n-C₃F₇COCl reacts with (Ph₂PMe)₄Pt to give trans-(Ph₂PMe)₂Pt(COC₃F₇)Cl.