Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects.
The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.
Institut für Organische Chemie, Technische Universität Dresden, 01062 Dresden, Germany.
Markus
M
Drees
Thomas
T
Strassner