Molecular mechanism of direct alkene oxidation with nitrous oxide: DFT analysisстатья

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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.

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[1] Avdeev V. I., Ruzankin S. F., Zhidomirov G. M. Molecular mechanism of direct alkene oxidation with nitrous oxide: Dft analysis // Kinetics and Catalysis. — 2005. — Vol. 46, no. 2. — P. 177–188. Reaction paths are calculated by the DFT method in the B2LYP/6- 31G*approximation for direct oxidation of cyclohexene and butene with nitrous oxide into carbonyl compounds. Two possible reaction channels differing in their intermediate are analyzed. Two-step mechanisms are predicted for these reactions. Both steps are activated reactions. The first step of the first channel is the conversion of the initial reactants into the five-membered heterocycle 1,2,3-oxadiazole, -C-N=N-O-C-, via a transition state. The first step of the second channel leads from the reactants via a transition state to a three-membered heterocycle (epoxide), -C-O-C-. The second step is the decomposition of these intermediates through hydrogen transfer within the hydrocarbon backbone and the formation of the final products. The rate-limiting step in the oxidation of cyclohexene and butene is determined by the electronic structure of the -C-N=N-O-C- heterocycle and is independent of the structure of the other hydrocarbon moieties. The activation energies calculated for separate steps suggest that the first reaction channel, leading to carbonyl compound, is more favorable from the standpoint of energetics. Two reaction pathways are possible for butene-1 oxidation, one leading to a ketone and the other to an aldehyde. The ketone is predicted to dominate in the product. © 2005 MAIK "Nauka/Interperiodica". [ DOI ]

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