钌(II)配合物中 2-苯基吡啶的杂化与键拉伸互变异构现象。

Hybridization vs. bond stretching isomerism in Ru(II) cyclometalated complexes of 2-phenylpyridine.

机构信息

Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior s/n, Ciudad Universitaria, Coyoacán, Apdo. Post. 70-646, 04510 México D.F., Mexico.

出版信息

Molecules. 2011 Dec 22;17(1):34-47. doi: 10.3390/molecules17010034.

DOI:10.3390/molecules17010034

PMID:22193212

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6268727/

Abstract

The phenomenon of formation of two isomers, yellow and orange, of the cyclometalated Ru(II) complex, [Ru(o-C₆H₄-py)(MeCN)₄]⁺, was investigated by EELS spectroscopy and theoretical calculations. Both forms show very similar structures and spectroscopic properties, but slight differences in X-ray data and absorption between them were noted. No double minimum on the potential energy surface was found and thus these two forms cannot be considered as bond stretching isomers. However, the DFT study revealed the change in the hybridization of the carbon in trans-position of one of acetonitrile ligands. This effect can be responsible for the difference in colour. The results of the theoretical modelling coincide well with the experimental EELS data.

摘要

通过电子能量损失谱(EELS)光谱和理论计算研究了偕二氰基合钌(II)配合物[Ru(o-C₆H₄-py)(MeCN)₄]⁺形成两种异构体（黄色和橙色）的现象。这两种形式表现出非常相似的结构和光谱性质，但在 X 射线数据和吸收方面略有差异。在势能表面上未发现双势阱，因此这两种形式不能被认为是键拉伸异构体。然而，DFT 研究揭示了反式位置上一个乙腈配体的碳原子杂化方式的变化。这种效应可能是颜色差异的原因。理论建模的结果与实验 EELS 数据吻合良好。