Density Functional Method Studies on Configuration and Electronic Structure of R-ReO3

We performed a systematic densities functional(X3LYP) study on the configuration and electronic structures of a series of high valence organorhenium oxides(R-ReO35Ln).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°.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.