THE SYNCHRONOUS THERMAL-DECOMPOSITION MECHANISM OF AZOISOPROPANE

The mechanism for the thermal decomposition of trans-azoisopropane has been studied using nb initio quantum mechanical approaches. The structural optimization methods include self-consistent field (SCF) and two-configuration SCF (TCSCF). Contrary to some current thought, azoisopropane decomposes through a 'synchronous' pathway, forming N-2 and two isopropyl radicals: i.e., two C-N bonds break simultaneously. The stability of the isopropyldiazenyl radical has also been studied. The barrier E(a) for 2-C3H7N2 decomposition predicted at the DZP CCSD(T) level of theory is 1 . 8 kcal mol(-1), slightly smaller than the E(a) for methyldiazenyl radical CH3N2 predicted at the same level of theory.