Zinc cation catalyzed carbonyl hydrazine C[sbnd]N bond cleavage in flash pyrolysis of energetic compound

By doing first-principles based simulations, a reaction of zinc cation catalyzing the carbonyl hydrazine C[sbnd]N bond cleavage was verified by investigating the flash pyrolysis processes of carbohydrazide, carbohydrazide perchlorate and zinc carbohydrazide perchlorate (GTX) crystals. We propose a mechanism of nitrogen gas generation that, perchlorate anions release oxygen radicals to seize hydrogen atoms of carbohydrazide, then coordination with zinc facilitates the C[sbnd]N bond cleavage in carbohydrazide. The center single zinc cation of GTX decreases the barrier of C[sbnd]N bond cleavage. The lowest energy barrier of breaking C[sbnd]N bond is 127.33 kJ mol⁻¹. The simulations reveal how the oxidizing perchlorate anion and the center metal contribute to the flash pyrolysis of GTX via the zinc cation catalyzed carbonyl hydrazine C[sbnd]N bond cleavage. The catalytic mechanism of transition metal in primary explosives opens new windows for designing coordination energetic compounds.