物理化学学报 >> 2011, Vol. 27 >> Issue (10): 2282-2290.doi: 10.3866/PKU.WHXB20111012

理论与计算化学 上一篇    下一篇

(1,3,5-C3P3H3)M与(1,3,5-C3P3H3)2M (M=Ti, V, Cr)配合物的结构与芳香性

刘玉宁1, 刘子忠1, 李伟奇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, 功能材料物理与化学自治区重点实验室, 呼和浩特 010022;
    2. 哈尔滨工业大学物理系, 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
  • 收稿日期:2011-04-20 修回日期:2011-06-23 发布日期:2011-09-27
  • 通讯作者: 刘子忠 E-mail:zizhliu@yahoo.com.cn
  • 基金资助:

    内蒙古自治区自然科学基金(20080404MS0203)资助项目

Structures and Aromaticities of Complexes (1,3,5-C3P3H3)M and (1,3,5-C3P3H3)2M (M=Ti, V, Cr)

LIU Yu-Ning1, LIU Zi-Zhong1, LI Wei-Qi2, LIU Dong-Sheng3, GE Xiang-Wei3   

  1. 1. College of Chemistry and Environmental Science, Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials, Inner Mongolia Normal University, Hohhot 010022, P. R. China;
    2. Department of Physics, Harbin Institute of Technology, Harbin 150080, P. R. China;
    3. College of Computer and Information Engineering, Inner Mongolia Normal University, Hohhot, 010022, P. R. China
  • Received:2011-04-20 Revised:2011-06-23 Published:2011-09-27
  • Contact: LIU Zi-Zhong E-mail:zizhliu@yahoo.com.cn
  • Supported by:

    The project was supported by the Natural Science Foundation of Inner Mongolia, China (20080404MS0203).

摘要: 运用密度泛函理论研究了(1,3,5-C3P3H3)M 和(1,3,5-C3P3H3)2M (M=Ti, V, Cr) 的结构、键合能以及芳香性. 结果表明: 低自旋的(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M基态结构分别具有C3vD3h对称性. 金属与配体间为共价作用, 二者之间存在σ、πδ三种成键方式. V的三明治配合物的解离方式与Ti 和Cr 的三明治配合物不同, 前者为分步解离, 后两者则为一步解离. 其中(1,3,5-C3P3H3)2Cr (D3h)的第一解离能最大, 配合物最稳定. 这些三明治和半三明治配合物都具有中心芳香性、内芳香性和外芳香性, 且中心芳香性均大于自由配体(1,3,5-C3P3H3)的中心芳香性. 芳香性主要贡献来源于π键和金属原子的孤对电子. 内芳香性按照Ti、V、Cr 的顺序依次增大, 且内芳香性明显要大于外芳香性. 高自旋的半三明治(1,3,5-C3P3H3)Ti (C3, 5A1) 与单重态(1,3,5-C3P3H3)Ti (C3v, 1A1) 相比, 配体的变形性增大, 稳定性增加, 且C平面中心芳香性和内芳香性均增大, 但P平面的中心芳香性却降低.

关键词: 密度泛函理论, 三明治配合物, 结构, 芳香性

Abstract: The equilibrium geometries, binding energies and aromaticities of (1,3,5-C3P3H3)M and (1,3, 5-C3P3H3)2M (M=Ti, V, Cr) were calculated by density function theory. The results indicate that the ground states of (1,3,5-C3P3H3)M and (1,3,5-C3P3H3)2M have C3v and D3h symmetries, respectively. The main interactions between the ligands and metal are covalent interactions featuring three types of interactions represented as σ, π and δ between the ligands and the metal. The dissociation method of the ligands and the metal in sandwich V complexes is different from that of Ti and Cr complexes, i.e., the former consists of two steps and the latter consists of one step. The first dissociation energy of (1,3,5-C3P3H3)2Cr is the largest and so it is the most stable one. These complexes have central, inner and outer aromaticities and the central-aromaticities of the complexes are stronger than that of (1,3,5-C3P3H3). The contributions of aromaticities is dominated by π bonds and the lone pair electronics of the metal atom. The inner-aromaticities of the complexes increase in the following order: Ti, V, Cr, and they are evidently stronger than the outer-aromaticities. Compared with (1,3,5-C3P3H3)Ti (C3v, 1A1) the distortion of the ligands for the high spin multiplicity of half-sandwich (1,3,5-C3P3H3)Ti (C3, 5A1) is larger and more stable. The central and inner aromaticities in the C plane of the high spin multiplicity half-sandwich (1,3,5-C3P3H3)Ti (C3, 5A1) are stronger than that of (1,3,5-C3P3H3)Ti (C3v, 1A1), but the central aromaticity in the P plane is weaker.

Key words: Density functional theory, Sandwich complex, Structure, Aromaticity

MSC2000: 

  • O641