EPR and ENDOR spectroscopic study of the reactions of aromatic azides with gallium trichloride?

Organic & Biomolecular Chemistry Pub Date: 2010-08-24 DOI: 10.1039/C0OB00084A

Abstract

The reactions of gallium trichloride with phenyl and deuterio-phenyl azides, as well as with 4-methoxyphenyl azide and deuterium isotopomers, were examined by product analysis, CW EPR spectroscopy and pulsed ENDOR spectroscopy. The products included the corresponding anilines together with 4-aminodiphenylamine type dimers, and polyanilines. Complex CW EPR spectra of the radical cations of the dimers [ArNHC6H4NH2]+˙ and trimers [ArNHC6H4NHC6H4NH2]+˙ were obtained. These EPR spectra were analysed with the help of data from the deuterium-substituted analogues as well as the pulse Davies ENDOR spectra. DFT computations of the radical cations provided corroborating evidence and suggested the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed.

Graphical abstract: EPR and ENDOR spectroscopic study of the reactions of aromatic azides with gallium trichloride
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