Laboratorium für Physikalische Chemie, ETH Zürich, Wolfgang-Pauli-Str. 10, CH-8093 Zürich, Switzerland.
Chemphyschem. 2010 Jun 21;11(9):1876-87. doi: 10.1002/cphc.201000121.
We examine calculated vibrational Raman optical activity (ROA) spectra of octahedral cobalt complexes containing different combinations of acetylacetonato and 3-acetylcamphorato ligands. Starting from the Delta-tris(acetylacetonato)cobalt(III) complex, the ROA spectra of isomers generated by successive replacement of acetylacetonato ligands by chiral (+)- or (-)-3-acetylcamphorato ligands are investigated. In this way, it is possible to assess the influence of the degree of ligand substitution, ligand chirality, and geometrical isomerism on the ROA spectra. In addition, the effect of the Lambda-configuration is studied. It is found that the ROA spectra contain features that make it possible to identify each of the isomers, demonstrating the great sensitivity of ROA spectroscopy to the chiral nature of the various complexes.
我们研究了含有不同乙酰丙酮酸盐和 3-乙酰莰酮酸盐配体组合的八面体钴配合物的计算振动拉曼旋光活性（ROA）光谱。从 Delta-三（乙酰丙酮酸盐）三钴（III）配合物开始，通过连续取代乙酰丙酮酸盐配体为手性（+）或（-）-3-乙酰莰酮酸盐配体来研究异构体的 ROA 光谱。通过这种方式，可以评估配体取代程度、配体手性和几何异构性对 ROA 光谱的影响。此外，还研究了 Lambda-构型的影响。结果发现，ROA 光谱包含可以识别每种异构体的特征，证明 ROA 光谱对各种配合物的手性性质具有很高的灵敏度。
