Reactions of low-valent metal complexes with fluorocarbons. Part 32. Tris-µ-(t-butyl isocyanide)-tris(t-butyl isocyanide)-triangulo-triplatinum
Abstract
Reaction of [Pt3(ButNC)6](1) with hexafluoroacetone affords the five-membered ring metallacycle [{[graphic omitted](CF3)2}(ButNC)2], but with tetrafluoroethylene an octafluorodiplatinacyclohexane complex [(ButNC)2[graphic omitted]F2] is formed, which undergoes dynamic behaviour in solution. Treatment of (1) with hexafluoropropene, octafluorobut-2-ene, and 1,1-dicyano-2,2-bis(trifluoromethyl) ethylene yields the three-membered ring complexes [{[graphic omitted]F(CF3)}(ButNC)2], [{[graphic omitted]F(CF3)}(ButNC)2], and [{[graphic omitted](CN)2}(ButNC)2], respectively. Whereas bromotrifluoroethylene and (1) form trans-[PtBr(CF:CF2)(ButNC)2], chlorotrifluoroethylene affords [([graphic omitted]FCl)(ButNC)2] which in solution rearranges to cis-[PtCl(CF:CF2)(ButNC)2] and subsequently to trans-[PtCl(CF:CF2)(ButNC)2]. Fluorine-19 n.m.r. and i.r. studies reveal that cis-[PtCl(CF:CF2)(ButNC)2] reverts to the η2-chlorotrifluoroethylene complex [([graphic omitted]FCl)(ButNC)2] on recrystailisation of the former from solutions.