Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals?

Molecules

Martí Gimferrer¹  Pedro Salvador¹  Gerard Comas-Vil๠

[1] Departament de Química and Institut de Química Computacional i Catàlisi, Universitat de Girona, Maria Aurèlia Capmany 69, 17003 Girona, Spain;

关键词: oxidation states;    localized orbitals;    metal carbenes;    wavefunction analysis;   

DOI  :  10.3390/molecules25010234

来源: DOAJ

【 摘 要 】

The use of centroids of localized orbitals as a method to derive oxidation states (OS) from first-principles is critically analyzed. We explore the performance of the closest-atom distance criterion to assign electrons for a number of challenging systems, including high-valent transition metal compounds, π-adducts, and transition metal (TM) carbenes. Here, we also introduce a mixed approach that combines the position of the centroids with Bader’s atomic basins as an alternative criterion for electron assignment. The closest-atom criterion performs reasonably well for the challenging systems, but wrongly considers O-H and N-H bonds as hydrides. The new criterion fixes this problem, but underperforms in the case of TM carbenes. Moreover, the OS assignment in dubious cases exhibit undesirable dependence on the particular choice for orbital localization.

【 授权许可】

Unknown