含穿透配体Y—Y键的反夹心配合物[Y—C8H8—Y]2+和L[Y—C8H8—Y]L(L=F, Cl, Br, I, Cp)的理论研究

doi:10.7503/cjcu20160586

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (11): 2006.doi: 10.7503/cjcu20160586

含穿透配体Y—Y键的反夹心配合物[Y—C₈H₈—Y]²⁺和L[Y—C₈H₈—Y]L(L=F, Cl, Br, I, Cp)的理论研究

刘楠楠¹(), 于爽², 丁益宏²()

1. 哈尔滨商业大学食品工程学院, 化学中心, 哈尔滨 150076
2. 吉林大学理论化学研究所, 长春 130021

收稿日期:2016-08-17 出版日期:2016-11-10 发布日期:2016-10-18
作者简介:联系人简介: 刘楠楠, 女, 博士, 讲师, 主要从事理论化学研究. E-mail: liunannyl@163.com;丁益宏, 男, 博士, 教授, 主要从事理论化学研究. E-mail: yhdd@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21301041, 51476049, 21273093, 21473069, 21073074)和黑龙江省自然科学基金(批准号: B201409)资助

Theoretical Studies on the [Y—C₈H₈—Y]²⁺ and L[Y—C₈H₈—Y]L (L=F, Cl, Br, I, Cp) Inverse Sandwiches with Y—Y Bond Passing Through the Ligand^†

LIU Nannan^1,^*(), YU Shuang², DING Yihong^2,^*()

1. Chemistry Center, College of Food Engineering, Harbin University of Commerce, Harbin 150076, China
2. Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China

Received:2016-08-17 Online:2016-11-10 Published:2016-10-18
Contact: LIU Nannan,DING Yihong E-mail:liunannyl@163.com;yhdd@jlu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21301041, 51476049, 21273093, 21473069, 21073074) and the Natural Science Foundation of Heilongjiang Province, China(No;B201409)

摘要/Abstract

摘要：

对反夹心配合物[Y—C₈H₈—Y]²⁺和L[Y—C₈H₈—Y]L(L=F, Cl, Br, I, Cp)进行了理论研究. 计算结果表明, 反夹心配合物的单态异构体为基态, 异构化稳定性较好. [Y—C₈H₈—Y]²⁺和L[Y—C₈H₈—Y]L(L=Cl, Br, I)中含有明显的穿透C₈H₈配体中心孔洞的Y—Y金属键, 而在F[Y—C₈H₈—Y]F中Y—Y键较弱. 此外, 多层夹心配合物Cp[Y—C₈H₈—Y]Cp(Cp=C₅H₅)中也含有穿透中心配体的Y—Y金属键; 另外, Y—Y键越强配合物的解离能越大, 这种穿透配体的成键对于反夹心配合物的稳定性具有显著的贡献.

关键词: 有机金属, 芳香性配体, 金属-金属键, 过渡金属, 钪族

Abstract:

The inverse sandwiches [Y—C₈H₈—Y]²⁺ and L[Y—C₈H₈—Y]L(L=F, Cl, Br, I) were theoretically investigated. The calculated results show that the singlet isomers with inverse sandwich configuration are the ground states, which are relatively stable against isomerization. [Y—C₈H₈—Y]²⁺and L[Y—C₈H₈—Y]L(M=Cl, Br, I) have distinct Y—Y metallic bond passing through the center hole of C₈H₈ ligand, yet the Y—Y interaction in F[Y—C₈H₈—Y]F is very weak. Besides, the multiple-decker sandwich Cp[Y—C₈H₈—Y]Cp(Cp=C₅H₅) also has Y—Y metallic bond passing through the center ligand. The results also show that the stronger the Y—Y bond is, the higher the dissociation energy of coordinated complex is. The bond passing through the ligand makes a noticeable contribution to the stability of inverse sandwiches.

Key words: Organic metal, Aromatic ligand, Metal-metal bond, Transition metal, Scandium family

中图分类号:

O641

TrendMD:

刘楠楠, 于爽, 丁益宏. 含穿透配体Y—Y键的反夹心配合物[Y—C₈H₈—Y]²⁺和L[Y—C₈H₈—Y]L(L=F, Cl, Br, I, Cp)的理论研究. 高等学校化学学报, 2016, 37(11): 2006.

LIU Nannan, YU Shuang, DING Yihong. Theoretical Studies on the [Y—C₈H₈—Y]²⁺ and L[Y—C₈H₈—Y]L (L=F, Cl, Br, I, Cp) Inverse Sandwiches with Y—Y Bond Passing Through the Ligand^†. Chem. J. Chinese Universities, 2016, 37(11): 2006.

图/表 3

Fig.1 Relative energies(kJ/mol) of [C8H8Y2]2+ and [C8H8Y2]L2 isomers(L=F, Cl, Br, I) obtained at PBEPBE/def2-TZVPPD//PBEPBE/def2-TZVP and BP86/def2-TZVPPD//BP86/def2-TZVP level(in brackets)

Fig.2 Selected molecular orbitals(MOs) of [Y—C8H8—Y]2+, F[Y—C8H8—Y]F, and Br[Y—C8H8—Y]Br obtained at PBEPBE/def2-TZVP level(Isovalue=0.04)

Fig.3 Selected molecular orbitals(MOs) of Cp[Y—C8H8—Y]Cp(Cp=C5H5) obtained at PBEPBE/def2-TZVP level(Isovalue=0.04)

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含穿透配体Y—Y键的反夹心配合物[Y—C₈H₈—Y]²⁺和L[Y—C₈H₈—Y]L(L=F, Cl, Br, I, Cp)的理论研究

Theoretical Studies on the [Y—C₈H₈—Y]²⁺ and L[Y—C₈H₈—Y]L (L=F, Cl, Br, I, Cp) Inverse Sandwiches with Y—Y Bond Passing Through the Ligand^†

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