H/D exchange under mild conditions in arenes and unactivated alkanes with CD and DO using rigid, electron-rich iridium PCP pincer complexes.

The synthesis and characterization of an iridium polyhydride complex () supported by an electron-rich PCP framework is described. This complex readily loses molecular hydrogen allowing for rapid room temperature hydrogen isotope exchange (HIE) at the hydridic positions and the α-C-H site of the ligand with deuterated solvents such as benzene-d, toluene-d and THF-d. The removal of 1-2 equivalents of molecular H forms unsaturated iridium carbene trihydride () or monohydride () compounds that are able to create further unsaturation by reversibly transferring a hydride to the ligand carbene carbon.

Supermetal: SbF-mediated methane oxidation occurs by C-H activation and isobutane oxidation occurs by hydride transfer.

SbF is generally assumed to oxidize methane through a methanium-to-methyl cation mechanism. However, experimentally no H is observed, and the mechanism of methane oxidation has remained unsolved for several decades. To solve this problem, density functional theory calculations with multiple chemical models (mononuclear and dinuclear) were used to examine methane oxidation by SbF in the presence of CO leading to the methyl acylium cation ([CHCO]).