Unexpected Formation of an Organoplatinum(IV) Fluoride Complex in the Reaction of Pt(TMEDA)(CH₃)₂ with Perfluoro-<i>sec</i>-butyl Iodide

Instead of undergoing a conventional oxidative addition reaction, Pt(TMEDA)Me2 (1) reacts with perfluoro-sec-butyl iodide to afford a rare example of a terminal Pt(IV) fluoride complex, trans-Pt(TMEDA)(I)(F)Me2 (2), along with a mixture of the trans- and cis-isomers of perfluoro-2-butene. Trapping experiments with CH3OD result in significant quantities of CF3CF2CFDCF3, indicating the intermediacy of a perfluorocarbanion. Complex 2 has been characterized by X-ray diffraction, and a mechanism for its formation is proposed.