[(BCO)_5]_2M(M=Fe,Co,Ni)金属夹心化合物的结构  

Structure of [(BCO)_5]_2M(M=Fe,Co,Ni) Sandwich Compounds

作　　者：郝爱琴[1] 贾建峰[2] 

机构地区：[1]山西师范大学分析测试中心,山西临汾041004 [2]山西师范大学化学与材料科学学院,山西临汾041004

出　　处：《山西师范大学学报（自然科学版）》2011年第1期65-71,共7页Journal of Shanxi Normal University(Natural Science Edition)

基　　金：山西省回国留学人员科研资助项目

摘　　要：基于密度泛函理论B3LYP/6-311++G(d,p)方法,对(BCO)5-与3d过渡金属离子Fe2+,Co2+,Ni2+形成的夹层配合物进行了稳定性与结构方面的计算研究.计算结果表明,与Cp-具有等瓣相似性的(BCO)5-可以形成类似于二茂化合物的夹层配合物.[(BCO)5]2M(M=Fe,Co,Ni)的结合能小于相应Cp2M的结合能.对[(BCO)5]2Fe的电子结构进行了详细的分析,发现其前线轨道与Cp2Fe有着较大的不同.通过电子结构分析,很好地解释了为什么[(BCO)5]2Co的对称性是C2v,为什么[(BCO)5]2Ni是一个具有理想D5d对称性的三重态结构;三种标题化合物的结合能顺序为[(BCO)5]2Fe>[(BCO)5]2Co>[(BCO)5]2Ni.并给出了这一稳定性顺序的原因.Based on the B3LYP/6-311＋ ＋G（d,p） method of density functional theory,the structure and stability of the sandwich compounds formed by（BCO）-5 with 3d transition metal ion Fe2＋,Co2＋ and Ni2＋ are calculated and investigated.The results show that（BCO）-5 can form metallocene-like compound with 3d transition metal ion as its isolobel C5H-5（Cp-）.However,the calculations show that the binding energy of [（BCO）5]2M（M= Fe,Co,Ni） is smaller than that of corresponding Cp2M.Analysis about the frontier orbital indicates that [（BCO）5]2Fe has different electronic structure from Cp2Fe.Why [（BCO）5]2Co has C2v symmetry and why [（BCO）5]2Ni has a triplet ground state in D5d symmetry are explained based on the analysis of electronic structure.We found that the binding energy of [（BCO）5]2M has the order of [（BCO）5]2Fe [（BCO）5]2Co [（BCO）5]2Ni.This order also can be understand based on their electronic structures.

关 键 词：羰基硼 金属茂 结构与稳定性 密度泛函理论 

分 类 号：O631.11[理学—高分子化学]