Inorganic and Transition Metal Azides

Experimental and theoretical studies show that all covalent azides possess a nonlinear azide group They also rationalize this remarkable structural feature. We have seen that the most important non-covalent contributions in the covalently bound azides system (X-N1-N2-N3) are the pi-delocalization over the enure molecule and a strong negative hyperconjugation which donates electron density from the filled sigma(X-N1) orbital into the unfilled, antibonding pi* (N2-N3) orbital For transition metal azide complexes, a bent configuration and a small difference between the N-N bond lengths, generally the longer one being adjacent to the transition metal, were observed