论文部分内容阅读
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.
M06-L Functionalisation of Density Functional Theory for the Structure of Bis-Pd Terphenyl Complexes Coordinated by Different Aromatic Heterocycles (Benzene, Furan, Thiophene, Benzothiophene, Indole) and Methylated Aromatic Heterocycles The nature of the interaction between Pd-Pd and Pd ... π in complexes has been studied.According to the analysis of molecular surface electrostatic potential, atom theory in molecule, energy decomposition of chemical bond and natural bond orbital analysis, Pd ... π interaction mode and Pd-Pd bond and Pd ... π interaction. The results show that the electrostatic potential distribution of aromatic heterocycle determines the coordination mode between Pd_2 and aromatic ring. The heteroatoms in heterocyclic ring affect the Pd-Pd intensity , The Pd-Pd bond is gradually weakened by the order of the heteroatoms O, S, N; the interaction between Pd and aromatic heterocycle (Pd ... π) is a partial covalent interaction, the exchange determines the intensity of Pd ... π interaction and Nature. The -CH_3 substituent on the heterocyclic ring weakens the Pd-Pd bond and enhances the Pd ... π interaction.