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Ruthenium Tetraoxide Oxidations of Alkanes:  DFT Calculations of Barrier Heights and Kinetic Isotope Effects

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journal contribution
posted on 03.03.2006 by Markus Drees, Thomas Strassner
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.