(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

引用本文: 刘玉宁, 刘子忠, 李伟奇, 刘东升, 葛湘巍. (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[J]. 物理化学学报, 2011, 27(10): 2282-2290. doi: 10.3866/PKU.WHXB20111012 shu

Citation: LIU Yu-Ning, LIU Zi-Zhong, LI Wei-Qi, LIU Dong-Sheng, GE Xiang-Wei. Structures and Aromaticities of Complexes (1,3,5-C₃P₃H₃)M and (1,3,5-C₃P₃H₃)₂M (M=Ti, V, Cr)[J]. Acta Physico-Chimica Sinica, 2011, 27(10): 2282-2290. doi: 10.3866/PKU.WHXB20111012 shu

(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

基金项目:
内蒙古自治区自然科学基金(20080404MS0203)资助项目 (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C_3v和D_3h对称性. 金属与配体间为共价作用, 二者之间存在σ、π和δ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 (D_3h)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 (C_3v, 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:

English

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

1.
1. College of Chemistry and Environmental Science, Inner Mon lia Key Laboratory for Physics and Chemistry of Functional Materials, Inner Mon lia 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 Mon lia Normal University, Hohhot, 010022, P. R. China
Received Date: 20 April 2011
Available Online: 27 September 2011
Fund Project:
内蒙古自治区自然科学基金(20080404MS0203)资助项目

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 C_3v and D_3h 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 (C_3v, 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 (C_3v, ¹A₁), but the central aromaticity in the P plane is weaker.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

(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

English

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

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