Abstract
Syn carbonyl oxides generated in alkene ozonolysis have been implicated as sources of hydroxy radical (•OH) in the atmosphere. We report quantum chemical calculations at the B3LYP/6-31G(d,p), CBS-QB3, MPW1K/6-31+G(d,p), and CBS-APNO levels to characterize the reactivity of syn acetaldehyde oxide and its vinyl hydroperoxide isomer. The vinoxy radical formed upon vinyl hydroperoxide decomposition is converted to a chemically activated peroxy radical in the presence of O2. All methods besides MPW1K predict that this species undergoes a 1,4-hydrogen shift with an activation barrier of ∼20 kcal/mol and then decomposes to yield •OH. RRKM/Master equation calculations predict that this unimolecular reaction of the peroxy radical will compete significantly with its collisional stabilization even up to 1 atm pressure. This chemistry can partly account for the •OD radicals recently observed in the ozonolysis of alkenes with vinylic deuteriums. The CBS-QB3 and CBS-APNO methods predict relative energies that agree to ...
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