Chemistry of 2,5-diaminotetrazole.

1,5-Diaminotetrazole is one of the most prominent high-nitrogen tetrazole compounds described in the literature. Interestingly the isomer 2,5-diaminotetrazole is nearly undescribed due to its challenging synthetic routes. 2,5-Diaminotetrazol (1) was successfully synthesized via amination of 5-aminotetrazole followed by various purification steps to separate it from isomeric 1,5-diaminotetrazole. In addition to the extensive characterization of 2,5-DAT further derivates by protonation, methylation and amination of the tetrazole ring were synthesized and characterized. The resulting tri-functionalized, ionic tetrazolium derivatives were combined with energetic anions (nitrate, perchlorate, azide, 5,5'-bistetrazole-1,1'-diolate (BTO 2 - )) to adjust and tune the properties of each compound. All compounds were intensively characterized including IR and multinuclear NMR spectroscopy, thermal analysis through DTA, X-ray diffraction and sensitivity testing. The purity was verified by CHNO elemental analysis and the energetic properties were calculated using the EXPLO5 code and the calculated enthalpy of formation (CBS-4M).