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

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)].