The azidoborazines [Me3N3B2(Me)(2)B(N-3)] and [H3N3B3(N-3)(3)] were prepared from the combination of Me3SiN3 and the chloroborazines [Me3N3B2(Me)(2)BCl] and (H3N3B3Cl3). The compounds have been characterized by analytical and spectroscopic methods. The molecular structure of [H3N3B3(N-3)(3)] has been confirmed by single-crystal X-ray diffraction techniques: triclinic space group P (1) over bar with a = 8.579(1) Angstrom, b = 9.182(1) Angstrom, c = 12.043(1) Angstrom, alpha = 104.62(1)degrees, beta = 90.26(1)degrees, gamma = 110.74(1)degrees, and Z = 4. The thermal behavior of the azides have been examined by TGA/DTA. The explosion sensitivity of [H3N3B3(N-3)(3)], which contains 82.58% nitrogen by weight, has been accessed by drop weight impact, spark, and friction tests. These measurements indicate that [H3N3B3(N-3)(3)] is a relatively sensitive explosive. The Staudinger reactivity of the azides with Ph3P was examined, and [H3N3B3(N-3)(3)] was found to produce [Ph3P=NH2](N-3). The molecular structure of this compound was determined by single-crystal X-ray diffraction techniques: orthorhombic space group P2(1)2(1)2(1) with a = 10.649(2) Angstrom, b = 11.737(3) Angstrom, c = 13.364(4) Angstrom, alpha = beta = gamma = 90 degrees, Z = 4.