Mechanistic molecular motion of transition-metal mediated β-hydrogen transfer: quasiclassical trajectories reveal dynamically ballistic, dynamically unrelaxed, two step, and concerted mechanisms.

The transfer of a β-hydrogen from a metal-alkyl group to ethylene is a fundamental organometallic transformation. Previously proposed mechanisms for this transformation involve either a two-step β-hydrogen elimination and migratory insertion sequence with a metal hydride intermediate or a one-step concerted pathway. Here, we report density functional theory (DFT) quasiclassical direct dynamics trajectories that reveal new dynamical mechanisms for the β-hydrogen transfer of [Cp*RhIII(Et)(ethylene)]+.

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]).