物理化学学报 >> 2008, Vol. 24 >> Issue (10): 1811-1816.doi: 10.1016/S1872-1508(08)60074-1

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C59XH(X=N, B)与1,3-丁二烯Diels-Alder环加成反应的区域选择性

梁云霄, 尚贞锋, 许秀芳, 赵学庄   

  1. 宁波大学材料科学与化学工程学院, 新型功能材料及其制备科学国家重点实验室培育基地, 浙江 宁波 315211; 南开大学化学系, 天津 300071
  • 收稿日期:2008-03-31 修回日期:2008-07-02 发布日期:2008-10-08
  • 通讯作者: 梁云霄 E-mail:liangyunxiao@nbu.edu.cn

Regioselectivity of 1,3-Butadiene Diels-Alder Cycloaddition to C59XH(X=N, B)

LIANG Yun-Xiao, SHANG Zhen-Feng, XU Xiu-Fang, ZHAO Xue-Zhuang   

  1. State Key Laboratory Base of Novel Functional Materials and Preparation Science, College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang Province, P. R. China; Department of Chemistry, Nankai University, Tianjin 300071, P. R. China
  • Received:2008-03-31 Revised:2008-07-02 Published:2008-10-08
  • Contact: LIANG Yun-Xiao E-mail:liangyunxiao@nbu.edu.cn

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摘要： 应用半经验的AM1和密度泛函B3LYP/6-31G*方法对1,3-丁二烯与C59XH(X=N, B) Diels-Alder环加成反应的区域选择性进行理论研究, 选择一些有代表性的C59XH(X=N, B)的6—6键探讨环加成反应的机理. 1,3-丁二烯与C59NH进行的Diels-Alder反应, 随着加成位置远离C59NH的N原子, 活化能越来越低, 但都比1,3-丁二烯与C60相应反应的活化能高. 与此相反, 对于1,3-丁二烯与C59BH进行的环加成反应, 加成位置最靠近B原子的2,12/r-和2,12/f-过渡态的势垒最低, 并且比1,3-丁二烯与C60进行环加成反应的活化能约低18 kJ·mol-1, 其产物也是热力学最稳定的. 与C60相应的反应相比, C59NH和C59BH中N和B原子不同的电子性质对其邻位双键进行Diels-Alder环加成反应的活性产生了不同影响, 前者使反应活性降低, 后者使反应活性增强.

关键词: C59XH(X=N, B), Diels-Alder环加成, 区域选择性, AM1, DFT

Abstract: The regioselectivity of Diels-Alder cycloaddition of 1,3-butadiene to C59XH (X=N, B) has been studied theoretically by means of the semiempirical AM1 and DFT (B3LYP/6-31G*) methods. The mechanisms of the cycloaddition on some selected 6—6 bonds of C59XH (X=N, B) have been analyzed. For C59NH, the activation energies become lower with the addition site increasingly farther fromthe N atom; however, they are all higher than that of the reaction of 1,3-butadiene with C60. In contrast to C59NH, for the cycloaddition to C59BH, the activation energies corresponding to 2,12/r-and 2,12/f-transition states, in which the addition sites are the nearest ones to the B atom, are the lowest ones,and are lower than that of the reaction of 1,3-butadiene with C60 by over 18 kJ·mol-1, and the products corresponding to these two transition states are the most stable ones. The different electronic natures ofNandB atoms results in different effects on the Diels-Alder reactions of 1,3-butadiene with C59NH and C59BH; the former makes the reactivity of C59NH reduced and the latter makes the reactivity of C59BH enhanced, relative to that of C60.

Key words: C59XH(X=N, B), Diels-Alder cycloaddition, Regioselectivity, AM1, DFT