Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanismElectronic supplementary information (ESI) available: Additional PESs, Cartesian coordinates, mulliken populations and spin densities for all structures, TDDFT output for excited states #1-5 for species 1, and the complete list of authors for ref. 18. See DOI: 10.1039/c6dt00419a

DFT calculations were performed in an effort to evaluate the mechanism of O 2 insertion into the Pt-H bond of Tp Me 2 Pt IV Me 2 H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt III &z.rad; species followed by addition of O 2 to form Pt III OO&z.rad;. Subsequent radical propagation involving this Pt III OO&z.rad; species and an additional equivalent of the Pt IV starting material result in the formation of the observed Pt IV OOH and regeneration of the Pt III &z.rad;. In addition examination of the reaction between AIBN and the Pt IV hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations. DFT calculations were performed in an effort to evaluate the mechanism of O 2 insertion into the Pt-H bond of Tp Me 2 Pt IV Me 2 H catalyzed by AIBN or light.