Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF(3), 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 SF(4) undergoes a rapid oxidative addition at Pt(0) to yield trans‐[Pt(F)(SF(3))(IMes)(2)]. A photolytic reaction of SF(6) at [Pt(IMes)(2)] in the presence of IMes gave the fluorido complexes trans‐[Pt(F)(2)(IMes)(2)] and trans‐[Pt(F)(SF(3))(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 SOF(2) or XeF(2). 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)].