Direct Dynamics Trajectories Reveal Nonstatistical Coordination Intermediates and Demonstrate that σ and π-Coordination Are Not Required for Rhenium(I)-Mediated Ethylene C-H Activation.

The C-H activation reaction between Cp(PMe3)2Re and ethylene results in kinetic selectivity for the Re-vinyl hydride I over the thermodynamically more stable Cp(PMe3)2Re(η2-ethylene) π-complex II. While transition-state and variational transition-state structures were located for individual pathways leading to I and II, DFT and CCSD(T) energies predict a large kinetic selectivity of 102-104, which is incompatible with the experimental 10:1 ratio. DFT direct quasiclassical trajectories revealed that the transition states do not provide a qualitatively correct reaction mechanism or a quantitatively correct selectivity due to a nonstatistical σ-CH coordination intermediate that precedes the transition states for C-H activation and π coordination. Using metadynamics and quasiclassical direct dynamics, we show that trajectories for the reaction between Cp(PMe3)2Re and ethylene result in direct formation of either the Re-vinyl hydride I or the π-complex II. Trajectories leading to the Re-vinyl hydride skip σ-coordination and do not require π-coordination. Consistent with experiments, trajectory selectivity provides a relatively small kinetic selectivity for the Re-vinyl hydride.