Reagent-Dependent Formation of C-C and C-F Bonds in Pt Complexes: An Unexpected Twist in the Electrophilic Fluorination Chemistry

Cyclometalated platinum(II) complexes (C-P)Rt(Aryl)py undergo oxidative addition reaction upon treatment with electrophilic fluorination reagents, XeF(2) or N-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate, giving eventually products of C-C coupling. However, when aryl = mesityl, the two reagents give completely different products: the N-F salt still favors the C-C coupling reaction while XeF(2) gives the unprecedented benzylic fluorination of one of the ortho-methyl groups of the mesityl ligand.