RECENT DEVELOPMENTS IN THE CHEMISTRY OF COVALENT AZIDES

The experimental and theoretical chemistry of covalently bound azides is an area that has seen considerable renaissance over the past 10 yea rs. This review is not exhaustive in scope but rather focuses on and h ighlights certain aspects in this field. In particular, the stability and dissociation of HN, is discussed at a very high level of theory (C ASSCF and MCSCF-CI) and compared and contrasted with experimental data and results from ''medium''-level ab initio computations (MP2, B-LYP) . From these results credence is given to those values calculated for larger systems and heavy elements for which very high level computatio ns are not possible. The experimentally well-characterized covalent ha logen azides (XN(3), where X = F, Cl, Br, I) as well as the heavy-elem ent group-15 compound Sb(N-3)(3) are discussed. The review also includ es discussion of the bond properties of the highly unstable N-bound az ides ON-N-3 and (FSO2)(2)N-N-3. In the final chapter attention is draw n to the recently predicted and eventually experimentally verified elu sive species OCN-NCO, which is isoelectronic to the hitherto unknown d iazide N-6.