Journal Title
Title of Journal: Russ Chem Bull
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Abbravation: Russian Chemical Bulletin
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Authors: G A Bogdanchikov A V Baklanov D H Parker
Publish Date: 2009/08/05
Volume: 57, Issue: 9, Pages: 1837-1841
Abstract
A new class of reactions of molecular oxygen O2 + ZH3I → O2ZH3 + I Z = C Si proceeding by the mechanism of “inversion substitution” was investigated by quantum chemistry methods and the transition state theory TST The profiles of the potential energy surfaces PES along the reaction coordinate and the characteristics of transition states were calculated using the DFT approach with the B3LYP hybrid functional and the DZVP basis set The characteristics of the transition states were then used for TST calculations of the rate constants for the direct and reverse “inversion substitution” reactions and their temperature dependences in the temperature interval 273–2000 K The activation barriers to the substitution reactions under study were found to be substantially lower than the barriers to the abstraction reactions O2 + ZH3I → ZH2I + HO2 by 163 kcal mol−1 for Z = C and by 72 kcal mol−1 for Z = Si The results obtained show that the “inversion substitution” reactions dominate over the abstraction reactions in the interaction of molecular oxygen with carbon and siliconcentered iodides as well as probably many other substrates
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