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A Correlation for Establishing Solvolysis Rates of Aqueous Al(III) Complexes: A Possible Strategy for Colloids and Nanoparticles

Authors
Journal
Journal of Colloid and Interface Science
0021-9797
Publisher
Elsevier
Publication Date
Volume
251
Issue
1
Identifiers
DOI: 10.1006/jcis.2002.8406
Keywords
  • Aluminum Complexes
  • Polyoxocations
  • Water-Exchange Rates
  • Polarizable Continuum Model
  • Ab Initio Calculations
  • Aluminum (Hydr)Oxide Minerals
Disciplines
  • Mathematics

Abstract

Abstract We here examine whether rates of solvolysis for a range of aluminum complexes can be predicted semiempirically by correlating calculated values of Al–O bond lengths with rate coefficients. We focus on a series of mono- and bis-ligated aqueous aluminum monomers and three ε-Keggin-like aluminum polyoxocations, and we make no attempt to simulate transition states. The Al–O bond lengths were calculated by performing ab initio geometry optimizations using the polarizable-continuum model to estimate solvation effects. Both Hartree–Fock and density functional methods (B3LYP) were tested using several basis sets up to 6-31+G(d). We find a strong correlation between rate coefficients for mono-ligated aluminum monomers and bond lengths to hydration waters. We cannot extrapolate the correlation, however, to large ε-Keggin-like multimers or to bis-ligated complexes, which suggests that the activated equilibrium for exchange of a water molecule in these molecules is different than that in the simple monomers.

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