Fluorocarbon platinum complexes

Abstract

Tetrakis(triphenylphosphine)platinum in benzene solution reacts with the fluoro-olefins C₂F₄, C₂F₃Cl, C₂F₃CF₃, CF₂CCl₂, cyclo-C₄F₆, cyclo-C₆F₁₀, and CF₂:CFCF:CF₂ to yield crystalline complexes of molecular formula (Ph₃P)₂Pt(fluoro-olefin). A similar reaction occurs between tetrakis(methyldiphenylphosphine)platinum and C₂F₃Cl or C₂F₃Br. In refluxing n-butanol, the complexes (Ph₂PR)₂Pt(C₂F₃X)(X = Cl, Br; R = Ph, Me) rearrange, affording trans-(Ph₂PR)₂Pt(CF:CF₂)X. Trifluoromethylnitrosyl reacts with tetrakis(triphenylphosphine)platinum affording a paramagnetic compound (Ph₃P)₂Pt(CF₃)NO. Nickelocene reacts with trifluoromethylnitrosyl giving π-C₅H₅NiNO. The ¹⁹F n.m.r. spectra of the complexes (Ph₃P)₂Pt(fluoro-olefin) have been interpreted in terms of structures involving a rigid σ-bonded three-membered ‘metallo-cyclopropane’ ring.