物理化学学报2011，Vol.27Issue(10)：2282-2290,9.
(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
Structures and Aromaticities of Complexes (1,3,5-C3P3H3)M and (1,3,5-C3P3H3)2M (M=Ti, V, Cr)
摘要
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 D3/, symmetries, respectively. The main interactions between the ligands and metal are covalent interactions featuring three types of interactions represented as a, n and 5 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 n 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 evidentlystronger than the outer-aromaticities. Compared with (1,3,5-CjPjH3)Ti (C3v,1A1) the distortion of the ligands for the high spin multiplicity of half-sandwich (1,3,5-C,P,H3)Ti (G>, SA) is larger and more stable. The central and inner aromaticities in the C plane of the high spin multiplicity half-sandwich (1,3,5-CsP3H>)Ti (C3, 5A1) are stronger than that of (1,3,5-C3PiH3)Ti (3v11A1), but the central aromaticity in the P plane is weaker.关键词
密度泛函理论/三明治配合物/结构/芳香性Key words
Density functional theory/ Sandwich complex/ Structure/ Aromaticity分类
化学化工引用本文复制引用
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):2282-2290,9.基金项目
内蒙古自治区自然科学基金(20080404MS0203)资助项目 （20080404MS0203）
