Mechanism of Chromyl Chloride Alkane Oxidation

Modern electronic structure methods, including complete active space-perturbation theory to second order (CASPT2) and a range of density functional (DFT) methods, are used to characterize the intermediates and transition states associated with chromyl chloride alkane oxidation. Computed energetics for radical abstraction are found to be inconsistent with experimental activation energetics. The alcohol product is also found to be too endothermic to be viable. A novel zwitterionic direct pathway is characterized which, when coupled with a dinuclear complex, exothermically produces alcohol consistent with experiment.