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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (22): 2297-2304. 上一篇    下一篇

研究论文

E42-, [CoE4]＋和[P4CoE4]－ (E＝N～Bi)结构和芳香性的理论预测

刘子忠*,1，王宇婷1，田维全2，刘东升3，葛湘巍3   

  1. (1内蒙古师范大学化学与环境科学学院 内蒙古自治区功能材料物理与化学重点实验室 呼和浩特 010022)
    (2哈尔滨工业大学理论与模拟化学研究所 基础与交叉科学研究院 哈尔滨 150080)
    (3内蒙古师范大学计算机工程与信息学院 呼和浩特 010022)
  • 投稿日期:2010-01-29 修回日期:2010-06-22 发布日期:2010-07-22
  • 通讯作者: 刘子忠 E-mail:zizhliu@yahoo.com.cn
  • 基金资助:

    内蒙古自然科学基金资助

Theoretical Predictions on Structures and Aromaticities of , [CoE4]＋ and [P4CoE4]－ (E＝N～Bi)

Liu Zizhong*,1 Wang Yuting1 Tian Weiquan2 Liu Dongsheng3 Ge Xiangwei3   

  1. (1 College of Chemistry and Environmental Science, Inner Mongolia Key Laboratory of Physics and Chemistry of Function Material, Inner Mongolia Normal University, Hohhot 010022)
    (2 Institute of Theoretical and Simulational Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080)
    (3 Computer & Information Enigneering College, Inner Mongolia Normal University, Hohhot 010022)
  • Received:2010-01-29 Revised:2010-06-22 Published:2010-07-22
  • Contact: zizhong liu E-mail:zizhliu@yahoo.com.cn

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用密度泛函理论杂化密度泛函B3LYP方法研究了E42-,  [CoE4]＋和[P4CoE4]－ (E＝N, P, As, Sb, Bi)几何结构、键能及芳香性. 结果表明, , [CoE4]＋和[P4CoE4]－的基态结构分别具有D4h, C4v和C4v(交错型)对称性. 三明治配合物中, 金属与配体间存在σ, π和δ三种成键方式, P4与E4间相互影响较小. E4对P4中的P—P键长影响随着N, P, As, Sb, Bi顺序逐渐变长, 中心Co离子与E4间的键合能随N, P, As, Bi, Sb的顺序增大. 的环外具有弱芳香性, 其它 环中心及环外均为反芳香性. 除[CoN4]＋外, 其它[CoE4]＋中的E4环均具有较强的中心和内芳香性及弱的外反芳香性. [P4CoE4]－中的P4和E4均具有较大的中心、内和外芳香性, 且P4环芳香性随N, P, As, Sb, Bi顺序逐渐递增.

关键词: 三明治配合物, 结构, 芳香性, 密度泛函

The equilibrium geometries, bonding energies and aromaticity of the , [CoE4]＋ and [P4CoE4]－ (E＝N, P, As, Sb and Bi) were predicted with the hybrid density functional method B3LYP within density functional theory. The calculations showed that the ground states of , [CoE4]＋ and [P4CoE4]－ were in D4h, C4v and C4v (staggered) symmetries, respectively. There are three types of interactions σ, π and δ between the ligands and metal for the [P4CoE4]－ complexes. There is a little influence between P4 and E4, and the P—P bond length of P4 is longer with the order of N, P, As, Sb and Bi. The binding energies between Co3＋ and E4 in [P4CoE4]－ increase with the order N, P, As, Bi and Sb. All of the center and inner side of rings are anti-aromatic excluding that the outer of isolated is aromatic. Except for [CoN4]＋, all of E4 rings of [CoE4]＋ have strong center and inner aromaticity, and weak outer anti-aromaticity. All of center, inner and outer of P4 and E4 rings in [P4CoE4]－ are aromatic, and the aromaticity of P4 ring increases with the order of N, P, As, Sb and Bi in [P4CoE4]-.

Key words: sandwich complex, structure, aromaticity, density functional theory