| [Co(3,3-tri)(amp)Cl]2+四个经式异构体取代、重排反应及其与结构关系的研究 |
| Study on Structure and Reactivity of the Geometric Isomers in [Co(3,3-tri)(amp)Cl]2+ System |
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| 摘要: 对[Co(3,3-tri)(amp)Cl]2+四个几何经式异构体在不同条件下的取代及重排反应进行考察的实验结果表明,四个几何经式异构体碱性环境下的水解速率没有显著的差异,cis异构体比trans异构体约快20倍。实验中没有观察到面式异构体。在100℃二甲亚砜中加热的重排反应实验中可观察到异构体进行配体翻转的历程,如异构体m1-Cl转化为m4-Cl,m2-Cl转化为m3-Cl。m3和m4相对较稳定。利用量子化学从头计算法,在赝势基组RHF/LANL2DZ的水 |
| 关键词: 钴(Ⅲ)配合物 取代及重排 量化计算 构效关系 |
| 基金项目: |
| Abstract: The kinetics of base hydrolysis reveals that the cis(N*) mer-isomers (m1 or m2) are about 20-fold more re-active than the trans(N*) forms (m3 or m4), there is no significant difference in reactivities between the cis(N*) and trans(N*) mer-isomers. No facial isomers have been found in the experiments. Rearrangements for DMSO as solvent at 100℃ show ligand folding courses between the isomers, such as m1-Cl was observed to rearrange to m4-Cl or m2-Cl to m3-Cl. Relatively, m3 and m4 are stable. A comparison of the measured structural parameters with an ab initio computational result for m3[ZnCl4] and m4[ZnCl4] (RHF/LANL2DZ optimised structure) reveals an maximum error of ±3%. The results suggest that equilibrium distributions of the geometric isomers relates to ground energy of them and reactivities of the isomers relates to their total bond angle distortions. |
| Keywords: Co(Ⅲ) complex substitution and rearrangement calculation of quantum chemistry structure and reactivity |
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| 薛赛凤,祝黔江,陶朱.[Co(3,3-tri)(amp)Cl]2+四个经式异构体取代、重排反应及其与结构关系的研究[J].无机化学学报,2002,18(6):563-570. |
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