DFT studies on the reaction mechanism of cis-dioxoruthenium(VI)-mediated alkene oxidation

Density functional theory (DFT) calculations with the B3LYP functionals elucidated the reactivity, and mechanism of cis-dioxoruthenium(VI)-mediated alkene oxidation reaction. The most plausible reaction pathway was discussed as three distinct processes, including (1) the oxidative [3+2] cycloaddition reaction, (2) the reduction process from Ru(IV) to Ru(II), and (3) the ligand substitution to release the final product. The first process has been confirmed to be rate-determining one, since each distinct step is strongly exothermic. The electronic state of cis-dioxoruthenium(VI) and the change of the electronic state during the reaction processes are rationalized in this article.