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

Elena A Pritchina, Nina P Gritsan, Thomas Bally

Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia.

Physical chemistry chemical physics : PCCP 2006 Feb 14

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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.

Citation

Elena A Pritchina, Nina P Gritsan, Thomas Bally. Matrix isolation and computational study of the photochemistry of p-azidoaniline. Physical chemistry chemical physics : PCCP. 2006 Feb 14;8(6):719-27