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Visible Light Induced Oxygen Atom Transfer From No2 To (Ch3)3n in a cRyogenic Ar Matrix

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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.

Affiliations: 1: Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ohokayama, Meguro, Tokyo 152, Japan; 2: Graduate School of BASE (Bio-Applications and Systems Engineering), Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183, Japan


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