Synthesis and Properties of N7O+ (PREPRINT)
Abstract
The reaction of NOF2+SbF6- with an equimolar amount of HN3 in anhydrous HF solution at -45 degrees Celsius produces N3NOF+SbF6-. When an excess of HN3 is used in this reaction, N7O+SbF6- is formed. However, this compound could not be isolated as a solid and rapidly decomposed in a quantitative manner with N2O evolution to N5+SbF6-. This reaction represents a novel and more convenient synthesis for N5+SbF6- because NOF2+SbF6- is more readily accessible than N2F+SbF6- and the N5+ can be labeled in all five positions with 15N by the simple use of terminally singly-labeled N3-. The formation of the N7O+ cation was established by isotopic labeling experiments and theoretical calculations. It is shown that the addition of a second azido ligand to the same central atom allows attack of the negatively charged N-alpha atom of one ligand by the positively charged N-gamma atom of the second ligand, thereby greatly lowering the activation energy barrier towards decomposition and explaining why geminal diazides are much less stable than either mono-azides or vicinal di-azides.
Document Details
- Document Type
- Technical Report
- Publication Date
- Nov 23, 2009
- Accession Number
- ADA513706
Entities
People
- Jerry A. Boatz
- Karl O. Christe
- Ralf Haiges
- William W. Wilson
Organizations
- Air Force Research Laboratory