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采用二阶微扰理论(MP2)计算方法,在6-31++G(d,p)的基组下,对气相中正丁烯负离子与N2O反应的微观机理进行了较为系统的理论计算研究,并在相同基组下进一步用QCISD方法在MP2优化的几何构型基础上做了单点能校正.计算结果表明,正丁烯负离子有顺式和反式异构体,它们的伯碳和仲碳都可以与N2O反应,前者的反应有α-H抽提、β-H抽提、基于IM11和氧抽提路径.而α-H抽提为主要反应路径,产物是丙烯基重氮甲基负离子(cis-CH3CHCHCN-N-,trans-CH3CHCHCNN-).后者的反应有甲基H抽提、乙烯基H抽提、基于IM12’和氧抽提路径,其中甲基H抽提为主反应路径,产物是丁二烯负离子,相比之下,在仲碳位置上的反应更有利一些.抽提氧的反应路径也是主反应的竞争路径,其产物应该能被检测到.此外,不管是主反应路径还是次反应路径都是强放热过程.
The second order perturbation theory (MP2) is used to calculate the microscopic mechanism of the reaction of n-butene anions with N2O in the basic group of 6-31 ++ G (d, p) The single base energy can be corrected by the QCISD method under the same basis set. The calculated results show that the n-butene anion has both cis and trans isomers. Their primary carbon and secondary Carbon can react with N2O, the former with α-H extraction, β-H extraction, based on the IM11 and oxygen extraction pathways, and α-H extraction as the main reaction pathway, the product is propylene diazomethyl Negative ions (cis-CH3CHCHCN-N-, trans-CH3CHCHCNN-) The latter reaction methyl H extraction, vinyl H extraction, based on IM12 ’and oxygen extraction path, in which methyl H extraction as the main reaction Path, the product is butadiene anion, in contrast, in the secondary carbon position of the reaction is more favorable.Suction of oxygen in the reaction path is also the main reaction of the competition path, the product should be able to be detected.In addition, regardless of the The main reaction path or the secondary reaction path are strong exothermic process.