Visible-light-induced oxygen-atom transfer from NO2 to trimethylamine has been investigated in a low-temperature Ar matrix. The bimolecular reaction with the threshold wavelength of 610 nm is tentatively interpreted by a mechanism to form the intermediate products of (CH3)2NONO and CH3, or the final products of (CH3)2NOCH3 and NO. Further irradiation at shorter wavelength (457.9–514.5 nm) seems to cause the secondary photolysis of (CH3)2NONO into (CH3)2NO and NO, which is followed by the recombination of (CH3)2NO with CH3 coexisting in a cryogenic Ar matrix cage to produce N,N,O-trimethylhydroxylamine, (CH3)2NOCH3. The reaction mechanism proposed is different from those reported for CH3NH2/NO2 and (CH3)2NH/NO2, the reason of which is discussed in comparison of the potential energy surfaces of three amine/NO2 photolytic systems.
Research on Chemical Intermediates – Springer Journals
Published: Apr 15, 2009
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