Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes

Abstract

The electron-rich Pt complex [Pt(IMes)2] (IMes: [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinylidine]) can be used as precursor for the syntheses of a variety of fluorido ligand containing compounds. The sulfur fluoride SF4 undergoes a rapid oxidative addition at Pt0 to yield trans-[Pt(F)(SF3)(IMes)2]. A photolytic reaction of SF6 at [Pt(IMes)2] in the presence of IMes gave the fluorido complexes trans-[Pt(F)2(IMes)2] and trans-[Pt(F)(SF3)(IMes)2] along with trans-[Pt(F)(SOF)(IMes)2] and trans-[Pt(F)(IMes’)(IMes)] (IMes’: cyclometalated IMes ligand), the latter being products produced by reaction with adventitious water. trans-[Pt(F)(SOF)(IMes)2] and trans-[Pt(F)2(IMes)2] were synthesized independently by treatment of [Pt(IMes)2] with SOF2 or XeF2. A reaction of [Pt(IMes)2] with a HF source gave trans-[Pt(H)(F)(IMes)2], and an intermediate bifluorido complex trans-[Pt(H)(FHF)(IMes)2] was identified. Compound trans-[Pt(H)(F)(IMes)2] converts in the presence of CsF into trans-[Pt(F)(IMes’)(IMes)].