摘要
用ＲＨＦ／６－３１Ｇ＊解析梯度方法研究了单重态二氯硅烯与乙烯和甲醛环加成反应的机理，并用二级微扰方法对各构型能量进行了相关能校正．结果表明，两反应历程均由两步组成：（１）二氯硅烯与乙烯和甲醛分别生成了中间配合物，是无势垒的放热反应；（２）中间配合物异构化成产物二氯硅杂环丙烷和二氯硅杂环氧甲烷，其势垒经零点能校正分别为９７．４３和１０３．２９ｋＪ／ｍｏｌ（ＭＰ２／６－３１Ｇ＊／／６－３１Ｇ＊）
The mechanism of the cycloaddition reaction of singlet dichlorosilylene and ethylene or/and formaldehyde has been studied by RHF/6\|31G\+* gradient method. The electron correlation energies of all the structures are calculated by using second\|order Moller\|Plesset perturbation theory(MP2). The results show that the two reaction proceesses are both two steps: (1) dichlorosilylene and ethylene or/and formaldehyde form an intermediate complex respectively, which is a exothermal reaction with no barrier; (2) two intermediate complexes isomerized to the products respectively, the barriers of the two reactions are 97\^43 and 103\^29 kJ/mol at MP2/6\|31G\+*//6\|31G\+* with zero\|point energies correction level.\=
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1999年第4期612-615,共4页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
关键词
二氯硅烯
环加成
二氯硅杂环丙烷
环氧甲烷
Dichlorosilylene, Cycloaddition reaction, \%Ab initio\% calculation, Transition state
