R—ReO_3的构型和电子结构的密度泛函研究

Density Functional Method Studies on Configuration and Electronic Structure of R-ReO_3

在X3LYP/6-311+G(2d,p)的水平下系统地研究了一系列高价有机铼氧化物(R—ReO3.Ln)的几何构型和电子结构.研究结果表明,用X3LYP方法预测的几何结构与实验值符合得很好,键长的误差一般小于0.001 nm,而键角的误差小于1°.同时发现不同配位类型的R基和L配体显著影响铼氧化合物的酸性以及Re—O键能.应用NBO分析和前线轨道理论可以合理地阐明配体调变的实质.

We performed a systematic densities functional（X3LYP） study on the configuration and electronic structures of a series of high valence organorhenium oxides （ R-ReO3 · L,, ）. Our calculations show that X3LYP function can give a good description of rhenium oxide geometries. In most cases, the deviations of bond lengths from the experimental results are less than 0. 001 nm, while the errors of bond angels are around 1 o. We found that the Lewis acidity and the strength of the Re-O bond could be subtly tuned by various R groups as well as amine ligands such that rhenium oxo can play a versatile role in catalytic oxidation. These results are rationalized in terms of NBO analysis and frontier orbital theory.