Reactions of low-valent metal complexes with fluorocarbons. Part 31. Bis(η-cyclo-octa-1,5-diene)-platinum and -palladium, with fluoroolefins

Abstract

Reaction of bis(η-cyclo-octa-1,5-diene)platinum with C₂F₄ gives an octafluorodiplatinacyclohexane complex [Pt₂(µ-CF₂·CF₂)₂(1,5-C₈H₁₂)₂], which undergoes ligand-displacement reactions to form [Pt₂(µ-CF₂·CF₂)₂L₄][L = PEt₃; L₂= 1,2-C₆H₄(AsMe₂)₂]. Tris(η-bicyclo[2.2.1]heptene)platinum reacts with C₂F₄ to give the mononuclear species [[graphic omitted]F₂)(C₇H₁₀)₂], which with P(OMe)₃ and with 1,5-C₈H₁₂ forms, respectively, [[graphic omitted]F₂){P(OMe)₃}₂] and [Pt₂(µ-CF₂·CF₂)₂(1,5-C₈H₁₂)₂]. In contrast, [Pd(1,5-C₈H₁₂)₂] and C₂F₄ afford the four-ring system [(1,5-C₈H₁₂)[graphic omitted]d(1,5-C₈H₁₂)]. Chlorotrifluoroethylene undergoes a vinyl-rearrangement reaction on treatment with [Pt(1,5-C₈H₁₂)₂] yielding [PtCl(CF:CF₂)(1,5-C₈H₁₂)]. Hexafluoropropene rearranges on treatment with [M(1,5-C₈H₁₂)₂](M = Pt or Pd) to form [(1,5-C₈H₁₂)[graphic omitted](1,5-C₈H₁₂)]. In the case of the palladium system, the complex [[graphic omitted]F(CF₃)}(1,5-C₈H₁₂)] has also been isolated, and shown to be the precursor of the binuclear complex. Octafluorobut-2-ene, hexafluoroacetone, and 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene react with [Pd(1,5-C₈H₁₂)₂] to give the conventional products [[graphic omitted]F(CF₃)}(1,5-C₈H₁₂)], [[graphic omitted]}(1,5-C₈H₁₂)], and [[graphic omitted](CF₃)₂}(1,5-C₈H₁₂)].