| Autor: |
Keith, Jason M., Ye, Yixin, Wei, Haochuan, Buck, Matthew R. |
| Předmět: |
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| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 8/7/2016, Vol. 45 Issue 29, p11650-11656, 7p |
| Abstrakt: |
DFT calculations were performed in an effort to evaluate the mechanism of O2 insertion into the Pt–H bond of TpMe2PtIVMe2H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving HṖ loss to form a PtIIIṖ species followed by addition of O2 to form PtIIIOOṖ. Subsequent radical propagation involving this PtIIIOOṖ species and an additional equivalent of the PtIV starting material result in the formation of the observed PtIVOOH and regeneration of the PtIIIṖ. In addition examination of the reaction between AIBN and the PtIV 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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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