Polynitrogen Chemistry
Abstract
Under combined DARPA, AFOSR, NSF, and DOE sponsorship, we have continued our work in polynitrogen chemistry. We have successfully prepared and characterized numerous polyazido compounds, such as As(N3)3, Sb(N3)3, As(N3)5, Sb(N3)5, As(N3)6(-), Sb(N3)6(-), Te(N3)4, Te(N3)6(2-) P(N3)6(-), and B(N3)4(-), and have studied the combination of N5(+) with some of these among. Most of these compounds are extremely energetic and shock sensitive. We have studied the reactions of the NF4(+) and N2F3(+) cations with HN3 in HF solution. The synthesis of the N7(-) anion was also pursued by preparing and characterizing R3SiNCl2 and (R3Si)2NCl compounds. Although their chlorine atoms could not be replaced by azido groups, the reaction of the latter with HF/MF5 resulted in the isolation of salts of the novel monochloroammonium cation. Enthalpies of formation were calculated for gas phase N3, N3(-), N5+, and N3 from ab initio molecular orbital theory. Stability calculations were carried out for solid N5+N3 and N5(+)N5(-), using these values and lattice energy estimates. The possible existence of FN5 was studied both experimentally by FT-IR spectroscopy of the volatile decomposition products from the thermolysis of N5(+)2SnF6(2-) and computation ally using a RRKM analysis.
Document Details
- Document Type
- Technical Report
- Publication Date
- Apr 21, 2003
- Accession Number
- ADA415289
Entities
People
- Ashwani Vij
- Karl Christie
- Robert Corley
- Vandana Vij
- William L. Wilson