Beilstein J. Org. Chem.2010,6, 713–725, doi:10.3762/bjoc.6.84
of Chemistry, University of St. Andrews, EaStChem, St. Andrews, Fife KY16 9ST, UK 10.3762/bjoc.6.84 Abstract The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium
suggested that 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.
Keywords: aluminium; aromatic azides; ENDOR; EPR; gallium
atoms in the dimer from 1. This is exactly as would be expected from the greater extent of aromatic delocalisation in a dimer from 8. Clearly, however, more than one isomer is possible.
Pulse ENDOR spectrum of the intermediate from 4-fluorophenyl azide 6
Pulsed ENDOR experiments, based on the ESE effect