Synthesis, Characterization, and Energetic Properties of Diazido Heteroaromatic High-Nitrogen C−N Compound

• Published in: Journal of the American Chemical Society Vol. 127; no. 36; pp. 12537 - 12543
• Main Authors: Huynh, My Hang V, Hiskey, Michael A, Chavez, David E, Naud, Darren L, Gilardi, Richard D
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 14-09-2005
• Subjects: Azides - chemical synthesis; Azides - chemistry; Chemistry; Crystallography, X-Ray; Exact sciences and technology; Heterocyclic compounds; Heterocyclic Compounds - chemical synthesis; Heterocyclic Compounds - chemistry; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Heterocyclic Compounds, 3-Ring - chemistry; Models, Molecular; Molecular Structure; Nitrogen - chemistry; Organic chemistry; Preparations and properties; Thermodynamics; Triazines; Five membered ring; Nitrogen heterocycle; Azo hydrazono tautomerism; NMR spectrometry; Diazotization; Organic synthesis; Electrochemical properties; Six membered ring; Triazine derivatives; Triazole derivatives; Redox potential; Thermodynamic properties; Nucleophilic substitution; Heat of formation; Carbon 13; Ultraviolet visible spectrometry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0509735

The synthesis, characterization, and energetic properties of diazido heteroaromatic high-nitrogen C−N compound, 3,6-diazido-1,2,4,5-tetrazine (DiAT), are reported. Its normalized heat of formation (NΔH f), experimentally determined using an additive method, is shown to be the highest positive NΔH f compared to all other organic molecules. The unexpected azido-tetrazolo tautomerizations and irreversible tetrazolo transformation of DiAT are remarkable compared to all other polyazido heteroaromatic high-nitrogen C−N compounds, for example, 2,4,6-triazido-1,3,5-triazine; 4,4‘,6,6‘-tetra(azido)hydrazo-1,3,5-triazine; 4,4‘,6,6‘-tetra(azido)azo-1,3,5-triazine; and 2,5,8-tri(azido)-1,3,4,6,7,9,9b-heptaazaphenalene (heptazine).