Covalent Main group element azides

Covalent azides are challenging inorganic compounds for inorganic and theoretical chemists, which are long known compounds in inorganic chemistry.[1] For instance, HN₃ was initially synthesized by Curtius in 1890,[2] while halogen azides XN₃ (X = F, Cl, Br, I) were prepared between 1900 (IN₃)[3] and 1942 (FN₃).[4] Moreover, they have been subject to many computational studies in order to gain a detailed understanding of the nature of covalent bonding. Unfortunately, the structural characterization of covalent azides is typically hampered by their expressed shock and heat sensitivity and characterization techniques were almost limited to NMR, IR, photoelectron, microwave spectroscopy and electron diffraction. We recently applied the in sitiu crysatllization technique as powerfiul method foir the growth of single crysatls directly on the diffractomter and succeeded in the structural characterization of many heat- and shock-sensitive covalent azides.

References

[1] For recent review articles see: a) P. Portius, M. Davis, Coord. Chem. Rev. 2013, 257, 1011; b) W. P. Fehlhammer, W. Beck, Z. Anorg. Allg. Chem. 2013, 639, 1053.

[2] T. Curtius, Berichte 1890, 23, 3023-3033.

[3] A. Hantzsch, M. Schumann, Ber. Dtsch. Chem. Ges. 1900, 33, 522.

[4] J. F. Haller, Ph.D. Dissertation, Cornell University, 1942.