几种典型芳烃杂环配体对双Pd三联苯配合物结构和性质的影响  

Effects of several typical heterocyclic arenes ligands on the structures and properties of terphenyl diphosphine dipalladium(I) complexes

作　　者：闫秀丽[1] 张雪英[1,2] 孟令鹏[1,2] 李晓艳[1,2] 

机构地区：[1]河北师范大学化学与材料科学学院,石家庄050024 [2]河北省无机纳米材料重点实验室,石家庄050024

出　　处：《中国科学：化学》2016年第9期900-907,共8页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21372062;21373075);河北省自然科学基金(编号:B2016205042);河北省教育厅基金(编号:ZD20131053;ZD20131037)资助项目

摘　　要：采用密度泛函方法的M06-L泛函对由不同芳烃杂环(苯、呋喃、噻吩、苯并噻吩、吲哚)及甲基化芳烃杂环配位的双Pd三联苯配合物的结构及配合物中Pd-Pd和Pd…π作用的本质进行了研究.通过分子表面静电势分析、分子中的原子理论、化学键的能量分解分析和自然键轨道分析等方法,讨论了不同芳烃杂环对Pd…π作用模式及Pd-Pd键和Pd…π作用性质的影响.结果表明,芳烃杂环的静电势分布决定Pd_2与芳香环的配位方式;杂环中杂原子种类影响Pd-Pd强度,Pd-Pd键按杂原子O、S、N的顺序化学键逐渐减弱;Pd与芳烃杂环之间的作用(Pd…π)为部分共价相互作用,交换作用决定Pd…π作用的强度和性质.杂环上的-CH_3取代基减弱了Pd-Pd键,增强了Pd…π作用.The structures of dipalladium（I） terphenyl compounds,with different heterocyclic arenes and methylation of heterocyclic arenes（benzene,furan,thiophene,benzothiophene and indole） as ligands are studied in different theoretical methods.The coordinated modes between Pd2 group and heterocyclic arenes and the nature of Pd–Pd and Pd…π interactions have been investigated based on molecular electrostatic potential analysis,atoms in molecules theory,energy decomposition analysis and natural bond orbital analysis.The calculated results show that the coordinated modes between Pd2 group and heterocyclic arenes are determined by the electrostatic potential distribution of aromatic heterocyclic ligands.The heteroatoms in heterocyclic arenes affect the strength of Pd–Pd bond,and the strength of Pd–Pd bond decreases in the order of O,S,and N.The interactions of Pd2 and heterocyclic arenes belong to partially covalent character,and the strengths and characters of Pd…πinteractions are determined by the exchange interactions.The methyl groups on heterocyclic arenes weaken the strength of Pd–Pd bond,and strengthen the Pd…π interactions.

关 键 词：芳烃杂环 金属–金属键 金属…π作用 电子密度拓扑分析 自然键轨道 

分 类 号：O641.4[理学—物理化学]