高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (9): 1427.

• 论文 • 上一篇    下一篇

卡宾与醚C—H键插入反应的理论研究(Ⅱ)──二氯卡宾和二氟卡宾与二甲醚的插入反应

林启君1, 冯大诚1, 马万勇1,2   

  1. 1. 山东大学化学院, 济南 250100;
    2. 山东轻工业学院化工系, 济南 250100
  • 收稿日期:1999-06-04 出版日期:2000-09-24 发布日期:2000-09-24
  • 通讯作者: 林启君(1944年出生),男,硕士,副教授,从事活性中间体的理论及有机合成研究.
  • 基金资助:

    国家自然科学基金(批准号:29973021);高等学校博士点基金

Theoretical Studies on the C—H Bond Insertion Reaction of Carbenes with Ethers (Ⅱ) Insertion Reactions of CX2(X=F, Cl) with Dimethylether

LIN Qi-Jun1, FENG Da-Cheng1, MA Wan-Yong1,2   

  1. 1. College of Chemistry, Shandong University, Jinan 250100, China;
    2. Department of Chemical Engineering, Shandong Institute of Light Industry, Jinan 250100, China
  • Received:1999-06-04 Online:2000-09-24 Published:2000-09-24

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摘要： 用量子化学从头算方法在MP2/6-31G(d)水平上研究了单重态的CX2(X=F,Cl)与二甲醚中C—H键的插入反应.两个体系的插入反应都是自发的,插入过程是CX2的亲电-亲核过程.CX2与二甲醚的插入势垒分别为125.9kJ/mol(经零点能校正后为132.2kJ/mol,X=Cl)和255.3kJ/mol(经零点能校正后为257.6kJ/mol,X=F).CF2的插入反应实际上难以发生.

关键词: 二氯卡宾, 二氟卡宾, 二甲醚, 插入反应, 从头计算

Abstract: The insertion reactions between singlet CX2(X=Cl, F) and C—Hbonds of dimethyl ether have been calculated at the MP2/6-31G(d) level by using ab initio molecular orbital theory. Both the two insertion reactions are spontaneous and the course of the insertion is electophilic-neucleophilic one for CX2. The potential barriers are 125.9 kJ/mol(133.2 kJ/mol after zero-point energy correction, X=Cl) and 255.3 kJ/mol(257.6 kJ/mol after zero-point energy correction, X=F), respectively. In fact, it is very difficult for CF2 to undergo insertion reaction at room temperature.

Key words: Dichlorocarbene, Difluorocarbene, Dimethyl ether, Insertion reaction, Ab initio calculation

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