Hanauer H, Puchta R, Clark T, van Eldik R (2007)
Publication Status: Published
Publication Type: Journal article
Publication year: 2007
Publisher: American Chemical Society
Book Volume: 46
Pages Range: 1112-1122
Journal Issue: 4
DOI: 10.1021/ic061284c
Density functional theory calculations have been performed for the water exchange mechanism of aquated Al(III). The effect of pH was considered by studying the exchange processes for [Al(H2O)(6)](3+) and its conjugated base, [Al(H2O)(5)OH](2+). Both complexes were found to exchange water in a dissociative way with activation energies (E-A) of 15.9 and 10.2 kcal/mol, respectively. The influence of solvent molecules on the gas-phase cluster model was considered by the addition of up to four water molecules to the model system. The stabilizing effect of the solvent on the transition state decreases E-A to 8.6 (hexa-aqua complex) and 7.6 (monohydroxo complex) kcal/mol, whereas E-A for all hydroxo species is consistently significantly lower than those for the related aqua systems, which indicates a much faster water exchange rate. For the hydroxo complex, all calculated five-coordinate intermediates, nH(2)O center dot[Al(H2O)(4)(OH)](2+) (n = 1, 2, 3, 4, 5), are more stable than the corresponding six-coordinate reactants. Our results therefore suggest the presence of a stable five-coordinate species of aquated Al(III), namely, the [Al(H2O)(4)(OH)](2+) complex.
APA:
Hanauer, H., Puchta, R., Clark, T., & van Eldik, R. (2007). Searching for stable, five-coordinate aquated Al(III) species. Water exchange mechanism and effect of pH. Inorganic Chemistry, 46(4), 1112-1122. https://dx.doi.org/10.1021/ic061284c
MLA:
Hanauer, Hans, et al. "Searching for stable, five-coordinate aquated Al(III) species. Water exchange mechanism and effect of pH." Inorganic Chemistry 46.4 (2007): 1112-1122.
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