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)Pt(Aryl)py undergo oxidative addition reaction upon treatment with electrophilic fluorination reagents, XeF₂ 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 XeF₂ gives the unprecedented benzylic fluorination of one of the ortho-methyl groups of the mesityl ligand.