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 (eta2-L)PtMe+ (based on DFT geometry optimization, L = [2.1.1]-2,6-pyridinophane) reacts with benzene to give (eta3-L) PtIV(Ph)2H+ and methane; the latter cation is in thermal equilibrium with the N-protonated PtII tautomer (eta2-L-H)Pt(Ph)2+, and these complexes react with ethane or cyclopentane to produce benzene and (L)PtH(olefin)+.
Vedernikov
Andrei N
AN
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
Caulton
Kenneth G
KG