Issue 39, 2014

The energetics of isomerisation in Keggin-series aluminate cations

Abstract

Electronic-structure calculations show that the ε-isomer of the polyoxoaluminate ion in the Keggin structure [AlO4-(Al(OH)2(H2O))12]7+ is the thermodynamically favoured one. Direct interconversion between the ε- and δ-isomers via cap rotation has a prohibitively high energy barrier in vacuo, suggesting that isomerisation in solution either proceeds via a dissolution–precipitation pathway, or that solvation and/or coordination to counterions reduces the barrier significantly. The implications for the formation of the [Al2O8Al28(OH)56(H2O)26]18+ ion are discussed.

Graphical abstract: The energetics of isomerisation in Keggin-series aluminate cations

Supplementary files

Article information

Article type
Communication
Submitted
14 Jun 2014
Accepted
08 Aug 2014
First published
08 Aug 2014

Dalton Trans., 2014,43, 14533-14536

Author version available

The energetics of isomerisation in Keggin-series aluminate cations

C. André Ohlin, J. R. Rustad and W. H. Casey, Dalton Trans., 2014, 43, 14533 DOI: 10.1039/C4DT01763C

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