H_2NNO_2裂解与重排反应的理论热力学、动力学研究

The Theoretically Thermodynamic and Kinetic Studies on the Scission and Rearrangement of NH_2NO_2

硝胺化合物的N—N键断裂和硝基-亚硝基重排(>N—NO_2→>N—ONO)是一类重要的化学反应。最近Golden等重新测定了DMNA[(CH_3)_2NNO_22]消失的速度常数,认为其分解应包括N—N键断裂和硝基-亚硝基重排后的再分解等过程,并得到分子束实验的确认,但理论研究尚不多见。Melius和McKee等都曾对该类体系进行过量化计算,但结果并不令人满意。Saxon等取其模型体系H_2NNO_2进行量化计算,似可定性说明其断裂。

Using the computational results of quantum chemistry at CI4d level, this paper has finished the thermodynamic and kinetic calculations theoretically for the reactionsThe results show, the rate of NH2O-NO scission is much larger than that of the rearrangement of NH2NO2 for the direction of nitro-nitrite rearrangement, while the N-NO2 bond scission and the rearrangement should be competed quite evenly. It is expected that factor A of them is larger The above results are all in agreement with Golden's experiment on DMNA [(CH3)2NNO2] basically, showing the thermodynamic and kinetic calculations on the system are successful. In addition, a set of thermodynamic functions of the reactions is given. All the results have never been found in literatures.