M. Nakata
Jul 1, 1994
Citations
0
Influential Citations
7
Citations
Journal
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Abstract
Abstract Red light-induced oxygen atom transfer from NO2 to 2,3-dimethyl-2-butene has been investigated in a low-temperature argon matrix. The IR spectra of a reaction intermediate indentified as an alkyl nitrite radical and two final products, tetramethyloxirane and 3,3-dimethyl-2-butanone (pinacolone), were observed. From analysis of the absorbance growth of the IR bands, first-order rate constants were determined by least-square fitting. Based on these results and those of our earlier works on NO2 photoreactions with other alkenes, a reaction mechanism is proposed that involves oxygen atom transfer from NO2 to the CC bond of 2,3-dimethyl-2-butene to give a short-lived singlet oxirane biradical. Alkyl nitrite radical is produced by a recombination of the transient biradical with NO trapped in the cage of the matrix. Tetramethyloxirane and pinacolone emerge from secondary photolysis of the trapped alkyl nitrite radical.