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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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Supplementary files

Article information


Submitted
02 Feb 2012
Accepted
10 Apr 2012
First published
17 Apr 2012

Dalton Trans., 2012,41, 10941-10947
Article type
Paper

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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