Synthesis, Characterization, and Reactivity of a Highly Oxidative Mononuclear Manganese(IV)-Bis(Fluoro) Complex.

Recently, transition-metal terminal nonoxo complexes have shown a remarkable ability to activate and functionalize C-H bonds via proton-coupled electron transfer (PCET). Here we report the first example of a mononuclear manganese(IV) bis(fluoro) complex bearing a tetradentate pyridinophane ligand, [Mn IV (TBDAP)(F) 2 ] 2+ ( 3 ), with an X-ray single crystal structure and physicochemical characterization. The manganese(IV) bis(fluoro) complex has a very high reduction potential of 1.61 V vs SCE, thereby enabling the four-electron oxidation of mesitylene to 3,5-dimethylbenzaldehyde. Kinetic studies, including the kinetic isotope effect and employment of other toluene derivatives, reveal the electron transfer (ET)-driven PCET in the C-H bond activation of mesitylene by 3 . This novel metal halide intermediate would be prominently valuable for expanding transition-metal halide chemistry.