Direct Dynamics Trajectories Demonstrate Dynamic Matching and Nonstatistical Radical Pair Intermediates during Fe-Oxo-Mediated C-H Functionalization Reactions.

The generally proposed mechanism for the reaction between non-heme Fe-oxo complexes and alkane C-H bonds involves a hydrogen atom transfer (HAT) reaction step with a radical pair intermediate that then has competitive radical rebound, dissociation, or desaturation pathways. Here, we report density functional theory-based quasiclassical direct dynamics trajectories that examine post-HAT reaction dynamics. Trajectories revealed that the radical pair intermediate can be a nonstatistical type intermediate without complete internal vibrational redistribution and post-HAT selectivity is generally determined by dynamic effects. Fast rebound trajectories occur through dynamic matching between the rotational motion of the newly formed Fe-OH bond and collision with the alkane radical, and all of this occurs through a nonsynchronous dynamically concerted process that circumvents the radical pair intermediate structure. For radical pair dissociation, trajectories proceeded to the radical pair intermediate for a very brief time, followed by complete dissociation. These trajectories provide a new viewpoint and model to understand the inherent reaction pathway selectivity for non-heme Fe-oxo-mediated C-H functionalization reactions.