Matrix isolation and computational study of the photochemistry of p-azidoaniline

Pritchina, Elena A.; Gritsan, Nina P.; Bally, Thomas

doi:10.1039/b511229j

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Journal article

Matrix isolation and computational study of the photochemistry of p-azidoaniline

Pritchina, Elena A. Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences and Novosibirsk State University, Novosibirsk, Russia
Gritsan, Nina P. Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences and Novosibirsk State University, Novosibirsk, Russia
Bally, Thomas Department of Chemistry, University of Fribourg, Switzerland

2006

Published in:

Physical Chemistry Chemical Physics. - 2006, vol. 8, p. 719-727

English 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.

Faculty

Faculté des sciences et de médecine

Department

Département de Chimie

Language