Thorium nanochemistry: the solution structure of the Th(iv)–hydroxo pentamer | Zendy

Clemens Walther | Zendy; Jörg Rothe | Zendy; Bernd Schimmelpfennig | Zendy; M. Fuss | Zendy

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

Author(s) -

Clemens Walther,

Jörg Rothe,

Bernd Schimmelpfennig,

M. Fuss

Publication year - 2012

Publication title -

dalton transactions

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.98

H-Index - 184

eISSN - 1477-9234

pISSN - 1477-9226

DOI - 10.1039/c2dt30243h

Subject(s) - pentamer , thorium , chemistry , solubility , x ray absorption fine structure , polymerization , mass spectrometry , nanochemistry , polymer , spectroscopy , crystallography , materials science , organic chemistry , chromatography , biochemistry , physics , uranium , quantum mechanics , metallurgy

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 Th(5)(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.

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