Roots of Acetate-Vanadium Linkage Isomerism: A QTAIM Study

• Type: Article in International Scientific Journal
• Date: 2016-04-04

Authors

Filipe Teixeira (Author) FCUP; Ricardo Mosquera (Author) Other; Andre Melo (Author) FCUP; Cristina Freire (Author) FCUP; Natalia N D S Cordeiro (Author) FCUP

Journal

Title: Inorganic Chemistry

Vol. 55

Pages: 3653-3662

ISSN: 0020-1669

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 8 Citations

Scopus - 8 Citations

Other information

Authenticus ID: P-00K-DBT

DOI: 10.1021/acs.inorgchem.6b00168

Abstract (EN): The possibility of linkage isomerism in a number of vanadium(IV) and vanadium(V) complexes with acetate was surveyed using Density Functional Theory (DFT) and Bader's Quantum Theory of Atoms in Molecules (QTAIM). The results show that vanadium-acetate linkages may be classified as bidentate symmetrical, bidentate asymmetrical, or monodentate, the latter being observed in about 40% of the cases. These latter ones correspond to situations where the two oxygen atoms of the acetate moiety are not equivalent. They are associated with an energy penalty of about 263 kJ.mol(-1), as determined by the distribution of the scaled kinetic energy of the atomic basins forming the acetate ligand. In the presence of bidentate symmetrical vanadium acetate linkages, the inner valence-shell charge concentrations on the vanadium atom deviate from the-traditional VSEPR-derived arrangement, with an energy penalty of about 780 kJ.mol(-1). A compromise situation is partially accomplished in the case of bidentate asymmetrical linkages, which allow a Gillespiean-like arrangement of the inner valence-shell charge concentrations. In this case, one of these local charge concentrations lies close to a V-O-ACO bond, which slightly disrupts the equivalence between the two oxygen atoms in the acetate ligand.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 10