N–PtIV–H/N–H...PtII intramolecular redox equilibrium in a product of H–C(sp2) cleavage and unusual alkane/arene C–H bond selectivity of ([2.1.1]pyridinophane)PtII(CH3)+

T-shaped 14 valence electron ((eta)2-L)PtMe+ (based on DFT geometry optimization, L = [2.1.1]-2,6-pyridinophane) reacts with benzene to give ((eta)3-L) PtIV(Ph)2H+ and methane; the latter cation is in thermal equilibrium with the N-protonated PtII tautomer ((eta)2-L-H)Pt(Ph)2+, and these complexes react with ethane or cyclopentane to produce benzene and (L)PtH(olefin)+.