[2.1.1]-(2,6)-Pyridinophane(L)-controlled alkane C–H bond cleavage: (L)PtMe2H+ as a precursor to the geometrically “tense” transient (L)PtMe+Electronic supplementary information (ESI) available: complete experimental and characterization data. See http://www.rsc.org/suppdata/nj/b3/b302055j/.

(η2-L)PtMe2 {L = [2.1.1]-(2,6)-pyridinophane} is protonated at Pt to give (η3-L)PtHMe2+, where three pyridine ligands of the macrocycle L bind to Pt in a facial manner. This cation eliminates methane at a rate convenient for trapping of the T-shaped, 14-valence electron (η2-L)PtMe+ (based on DFT geometry optimization) by ethane, propane, n-butane, cyclopentane and cyclohexane to give (η3-L)Pt(olefin)H+ and CH4. The crystal structure of (η3-L)Pt(cyclohexene)H+ as its BArF−4 salt is reported.