太原理工大学学报2017，Vol.48Issue(1)：1-10,10.DOI:10.16355/j.cnki.issn1007-9432tyut.2017.01.001
非手性单齿配体对反式双二胺合钴（Ⅲ）配合物圆二色谱的影响
Theoretical Study of the Influence of Achiral Unidentate Ligands on Electronic Ci rcular Dichroism of trans-(bis-Diamine) Cobalt(Ⅲ) Complexes
摘要
Abstract
To assess the influence of achiral unidentate ligands on electronic circular dichroism spectra ,the excitation energies ,oscillator and rotational strengths for a series of trans‐bis‐ethyl‐enediamine and propylenediamine cobalt (Ⅲ) complexes containing the unidentate ligands X (X=Cl- ,CN - ,NH3 ,NO2- ,N3- ,etc) have been calculated at the TDDFT level using the B3LYP functional and 6‐311+ + G(2d ,p) basis set .It was found that ,for the chelates with nonaxially symmetry unidentate ligands (X= N3- ,SCN - ,NO2- ) ,the chiral orientations (δ/λ) of the N3-and SCN - dominate the ECD spectra .However ,the contribution from the last one ligand is rela‐tively smaller than that of the first two .Such phenomenon has been successfully observed in the experimental ECD spectra .The δ‐orientation of NO2- exhibits one strong negative and another weak positive band shapes in the ECD curves ,and such distributions is consistent with the exper‐imental observation of trans‐[Co(pn)2 (NO2 )2 ]+ .For all of the chelates ,the ECD patterns in the long‐wavelength region are dependent on the spectrochemical series of the unidentate ligands X in the sequence from weak to strong :SCN - ,Cl- ,N3- ,H2O ,NCS - ,NH3 ,en ,NO2- ,CN - .The first absorption peak of the ECD spectra is negative in sign for the chelates with stronger unidentate ligands ,while it is positive in sign for the complexes with weaker unidentate ligands .关键词
非手性单齿配体/双二胺合钴配合物/含时密度泛函理论/手征光学性质/圆二色谱Key words
achiral unidentate ligands/bis-diamine cobalt complexes/TDDFT calculations/chi-roptical properties/ECD spectra分类
化学化工引用本文复制引用
贾杰,冯丽霞..非手性单齿配体对反式双二胺合钴（Ⅲ）配合物圆二色谱的影响[J].太原理工大学学报,2017,48(1):1-10,10.基金项目
国家自然科学基金资助项目手性配合物手征光学性质的理论分析和应用研究 （）
