A density functional theoretical study on solvated AI3+ -oxalate complexes: structures and theormodynamic properties

Adelia Aquino, Daniel Tunega, Georg Haberhauer, Martin Gerzabek , Hans Lischka

Publikation: Beitrag in FachzeitschriftArtikelBegutachtung

Abstract

Density functional theory calculations using split-valence polarized basis sets augmented by diffuse s and p functions an the carbon and oxygen atoms were carried out for the complexes of hydrated A13+ with oxalic acid. and the oxalate mono- and dianions. Monodentate and bidentate structures with up to three ligands have been computed. The polarized continuum model was used to study the solvent effect an the structures and stabilities of the complexes. Reaction energies for the replacement of water molecules in the aluminum-hexaaquo complex by oxalate ligands have been computed. Based an a detailed thermodynamical analysis, characteristic differences in the formation of mono- and bidentate structures were found. In the former case the entropy contributions to AG are rather small, whereas in the latter case they are substantial. Thus, the formation reactions for the monodentate complexes are energy-driven whereas those for the bidentate complexes are entropy-driven. In agreement with experiment, the most dominant complex in solution is [AlOx3]3-. From the complexes with oxalic acid and the partially deprotonated form HOx-, only the latter should give stable bidentate complexes in solution.
OriginalspracheEnglisch
Seiten (von - bis)2845-2850
Seitenumfang6
FachzeitschriftPhysical Chemistry Chemical Physics
PublikationsstatusVeröffentlicht - 2000

Research Field

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