The energetics of isomerisation in Keggin-series aluminate cations

• Electronic-structure calculations show that the e-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 epsilon- and delta-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.

Ämnesord

NATURVETENSKAP  -- Kemi -- Oorganisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

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