Recent developments in the chemistry of homoleptic azido complexes of the main group elements

The chemistry of covalent azides of main group elements has developed rapidly during the last decade. Interest in this area of pseudohalogen chemistry arises from both fundamental questions of bonding in unusual, highly nitrogen-rich molecules as well as potential practical applications. Especially binary azides and homoleptic azido complexes were at the forefront of new developments which tested the limits of preparative inorganic and computational chemistry. This paper reviews and discusses the syntheses, structures and spectroscopic properties (14N NMR, Raman and IR) of the homoleptic azido complexes with an emphasis on Groups 13–16.

► Recent synthetic approaches to homoleptic azido complexes examined and classified.
► 14N NMR, IR, Raman and X-ray data on many azido complexes have become available.
► Analytical data reveal trends in azide coordination that is critical to kinetic stability.