Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (10): 2282-2290.doi: 10.3866/PKU.WHXB20111012

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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