卡宾与醚C—H键插入反应的理论研究——(Ⅰ)卡宾与二甲醚的插入反应

Theoretical Studies on the C—H Bond Insertion Reaction of Carbenes with Ethers(Ⅰ) Insertion Reaction of Carbene with Dimethyl Ether

用量子化学从头计算方法在ＭＰ２／６－３１Ｇ（ｄ）水平上计算了单重态的ＣＨ２ 与二甲醚中Ｃ—Ｈ键插入反应的过程， 并在ＭＰ４／６－３１Ｇ（ｄ）水平上计算了反应物、过渡态和产物的能量．反应仅具有一个８．１ ｋＪ／ｍ ｏｌ的早期势垒， 反应过程是卡宾的一个亲电－亲核过程， 在插入过程中， 卡宾空的ｐ 轨道和占有一对孤电子的σ轨道分别指向Ｃ—Ｈ键的Ｈ原子和Ｃ原子．

The insertion reaction of singlet CH 2 with C—H bond in dimethyl ether has been calculated at MP2/6 31G(d) and MP4/6 31G(d)//MP2/6 31G(d) levels by using ab initio molecular orbital theory. The potential barrier of the reaction is an early one and only 8.1 kJ/mol. The process of the reaction is electrophilic nucleophilic one in connection with carbene. The empty p orbital and the occupied σ orbital by a lone electron pair of carbene point towards H atom and C atom of the C—H bond respectively.