含平面四配位碳镧系配合物结构的理论研究  

Studies of structures of lanthanide complexes with planar tetracoordinate carbons

作　　者：刘芳 张聪杰[1] LIU Fang;ZHANG Congjie(Key Laboratory of Macromolecular Science of Shaanxi Province,School of Chemistry Chemical Engineering,Shaanxi Normal University,Xi＇an 710119,Shaanxi,China)

机构地区：[1]陕西师范大学化学化工学院,陕西省大分子科学重点实验室,陕西西安710119

出　　处：《陕西师范大学学报（自然科学版）》2018年第5期56-64,76,共10页Journal of Shaanxi Normal University：Natural Science Edition

基　　金：国家自然科学基金(21373133)

摘　　要：利用密度泛函理论(DFT)研究了1-硼杂环[1.1.0]2(3)丁烯(1BB)和2-硼杂环[1.1.0]1(3)丁烯(2BB)衍生物作为配体与镧系金属形成(bis-1BB)LnCl_3和(bis-2BB)LnCl_3(Ln=Sc、Y、La、Nd、Sm、Dy、Ho、Yb和Lu)配合物的结构、稳定性、化学键和芳香性。计算结果表明,bis-1BB和bis-2BB与LnCl_3可以形成稳定的镧系金属配合物。在配合物(bis-1BB)LnCl_3和(bis-2BB)LnCl_3中,Ln—C和Ln—N的键长、电子密度和拉普拉斯值表明该化学键为共价键。其中,(bis-1BB)LnCl_3和(bis-2BB)LnCl_3(Ln=Sc、Y、La、Sm、Lu)中Ln—C和Ln—N的键长与(bis-NHC)LnCl_3接近,因此配体bis-1BB和bis-2BB与bis-NHC类似。镧系配合物中三元环和六元环中心的NICS(0)值表明,这些三元环和六元环具有较强的芳香性,特别是包含两个平面四配位碳(ptCs)的(bis-1BB)LnCl_3和(bis-2BB)LnCl_3配合物的形成在热力学上是稳定的。因此,研究从理论上得到了一种新型稳定的包含ptC的镧系金属配合物。Using density functional theory（DFT）,the structures,stability,chemical bonding and aromaticity of lanthanide complexes bearing the derivatives of 1-borabicyclo[1.1.0]but-2（3）-ene（1 BB）and 2-borabicyclo[1.1.0]but-1（3）-ene（2 BB）,（bis-1 BB）LnCl3 and（bis-2 BB）LnCl3（Ln=Sc,Y,La,Nd,Sm,Dy,Ho,Yb and Lu）,have been investigated.Calculated results indicate that bis-1 BB and bis-2 BB can coordinate with LnCl3 to form stable lanthanide complexes.The lengths of Ln—C and Ln—N bonds in（bis-1 BB）LnCl3 and（bis-2 BB）LnCl3,as well as the electron density and Laplacian values of Ln—C and Ln—N bonds in（bis-1 BB）LnCl3 and（bis-2 BB）LnCl3 show that Ln—C and Ln—N have covalent bond characteristic,in which the distances of Ln—C and Ln—N bonds in（bis-1 BB）LnCl3 and（bis-2 BB）LnCl3（Ln=Sc,Y,La,Sm and Lu）are close to those of in（bis-NHC）LnCl3.Thus,the bis-1 BB and bis-2 BB are analogous to the well-established bis-NHC.The NICS（0）values in the centers of the three-and six-membered rings of these lanthanide complexes show that the three-and six-membered rings have strong aromaticity.In particular,（bis-1 BB）LnCl3 and（bis-2 BB）LnCl3 complexes are thermodynamically favorable to be formed and contain two planar tetracoordinate carbons（ptCs）.Thus,a family of novel stable lanthanide complexes with ptC is theoretically obtained.

关 键 词：密度泛函理论 镧系配合物 平面四配位碳 稳定性 

分 类 号：O641[理学—物理化学]