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Issue 36, 2012
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Thorium nanochemistry: the solution structure of the Th(IV)–hydroxo pentamer

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Abstract

Tetravalent thorium exhibits a strong tendency towards hydrolysis and subsequent polymerization. Polymeric species play a crucial role in understanding thorium solution chemistry, since their presence causes apparent solubility several orders of magnitude higher than predicted by thermodynamic data bases. Although electrospray mass spectrometry (ESI MS) identifies Th(IV) dimers and pentamers unequivocally as dominant species close to the solubility limit, the molecular structure of Th5(OH)y polymers was hitherto unknown. In the present study, X-ray absorption fine structure (XAFS) spectroscopy, high energy X-ray scattering (HEXS) measurements, and quantum chemical calculations are combined to solve the pentamer structure. The most favourable structure is represented by two Th(IV) dimers linked by a central Th(IV) cation through hydroxide bridges.

Graphical abstract: Thorium nanochemistry: the solution structure of the Th(iv)–hydroxo pentamer

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Publication details

The article was received on 02 Feb 2012, accepted on 10 Apr 2012 and first published on 17 Apr 2012


Article type: Paper
DOI: 10.1039/C2DT30243H
Citation: Dalton Trans., 2012,41, 10941-10947
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    Thorium nanochemistry: the solution structure of the Th(IV)–hydroxo pentamer

    C. Walther, J. Rothe, B. Schimmelpfennig and M. Fuss, Dalton Trans., 2012, 41, 10941
    DOI: 10.1039/C2DT30243H

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