Abstract
The oxidation reactions of ethylene, propene, dimethyl sulfide, trimethylamine, and trimethylphosphine with peroxynitrous acid have been studied computationally with the B3LYP, MP2, MP4, CISD, QCISD, and QCISD(T) levels of theory. The activation barriers for the alkene (ethylene and propene) epoxidations (18.4 and 15.5 kcal/mol at the QCISD(T)/6-31G*//QCISD/6-31G* level, respectively) and for the oxidations of dimethyl sulfide, trimethylamine, and trimethylphosphine (8.3, 4.6, and 0.5 kcal/mol at the QCISD(T)/6-31G*//B3LYP/6-311G** level, respectively) with peroxynitrous acid are similar to the barriers of their oxidations with peroxyformic acid and dimethyldioxirane, although these peroxides have very diverse O−O bond dissociation energies. Therefore, the feasibility of alkene epoxidation and the oxidations of methyl-substituted sulfides, amines, and phosphines by peroxynitrous acid should not differ significantly from those for peroxyformic acid and dimethyldioxirane. The transition structures for the e...
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