We think that the title reaction proceeds by an addition-elimination mechanism at room temperature. At higher temperature, directive abstraction channel with N_2+ H_2CO products becomes a possible pathway. The present work assists the experimental worker to determine reaction products. 作者认为,反应在室温下是加成-消除机理,而在高温下可以通过直接取代的机理获得N2+H2CO。
Our calculations reveal that the addition-elimination mechanism is clearly preferred over the C-H bond activation mechanism thermodynamically and kinetically with VO2+ as the catalyst. The rate-determining step is the formation of the amino radical complex. 计算结果表明,VO2+作为催化剂时,加成消除机理和C-H键活化机理的决速步骤均为氨基复合物形成中的氢转移步骤,且加成消除机理要比C-H键活化机理要有利得多。
The predicted nuclear independent chemical shift ( NICS) values of benzene ring indicate that the benzene ring keeps its aromaticity throughout the addition-elimination mechanism. 苯环中心的核独立化学位移(NICS)值表明,加成消除机理中,所有驻点中苯部分或苯基中的苯环均保持其芳香性。
Except for the carbon-carbon double bond insertion mechanism, we also discover the other two mechanisms: olefinic carbon addition-elimination mechanism and side oxygen addition-elimination mechanism. 除了可能的碳碳双键插入反应机理以外,我们还发现了烷基碳加成-消除和端基氧加成-消除机理。