Matrix isolation and computational study of the photochemistry of p-azidoaniline.
The photochemistry of p-azidoaniline was studied in argon matrices in the absence and presence of oxygen. With the help of quantum chemical calculations we were able to characterize the triplet p-aminophenylnitrene as well as the cis- and trans-p-aminophenylnitroso oxides. It was found that the latter two isomers can be interconverted by selective irradiation and that they are ultimately converted into p-nitroaniline. Although restricted wavefunctions of the nitroso oxides are unstable, CASSCF calculations turned up no evidence for the claimed diradical character of these compounds. Also we found no evidence for dioxaziridines as intermediates of the conversion of the nitroso oxides to p-nitroaniline.
Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia.
Elena A
EA
Pritchina
Nina P
NP
Gritsan
Thomas
T
Bally
D000814:Aniline Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000528:radiation effects; D001128:Argon / Q000737:chemistry; D001391:Azo Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000528:radiation effects; D003198:Computer Simulation; D008956:Models, Chemical; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry; D010782:Photolysis; D011789:Quantum Theory; D014466:Ultraviolet Rays
D000814:Aniline Compounds; D001391:Azo Compounds; D009603:Nitroso Compounds; C070827:4-azidoaniline; D001128:Argon; D010100:Oxygen