二胺合铑类配合物CD光谱的结构规律研究  

Study on the Structural Relations of the CD Spectra of Tris-diamine Rhodium Chelates

作　　者：王建明[1] 王越奎[1] 王炎[1] 刘阳[1] 

机构地区：[1]山西大学分子科学研究所,山西太原030006

出　　处：《山西大学学报（自然科学版）》2008年第A01期99-102,共4页Journal of Shanxi University(Natural Science Edition)

基　　金：国家自然科学基金（20673069）;山西省自然科学基金（2007011021）

摘　　要：应用密度泛函理论，在DFT／B3LYP／SDD／／TDDFT／B3LYP／SDD水平上，系统计算了二胺合铑类配合物的激发能、转动强度和相应的圆二色（CD）光谱．对计算结果的定量分析表明，该类配合物的CD效应主要取决于RhN6配位八面体构型（△／∧）的影响，而配体环平面的折叠方式（δ/λ）和取代基空间位置（R／S）的影响可以忽略不计．特别是其特征d-d跃迁吸收带，△构型呈现出负的Cotton效应，而∧构型则为正的Cotton效应．这些规律为利用CD光谱直接测定溶液中有关配合物的绝对构型奠定了基础．Calculations of the excited state energies,rotatory strengths,and the CD spectra of trisdiamine rhodium chelates, were performed at the DFT/B3LYP/SDD//TDDFT/B3LYP/SDD level. It was found that the dominant CD effects reflect mostly the △/∧ core configuration; the contributions of δ/λ twists of the ligand rings and R/S chiral carbon atoms are negligible. Especially,the first Cotton effect originated from the d-d transitions is always negative for △ configurations, while it is positive for ∧ configurations. These findings make it possible to determine the absolute configuration （△/∧） of related chelates in solution directly from their CD spectra.

关 键 词：二胺合铑类配合物 圆二色光谱TDDFT计算 手征光学性质 

分 类 号：O641[理学—物理化学]