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First Structural Characterization of a Protactinium(V) Single Oxo Bond in Aqueous Media

Claire Le Naour,^† Didier Trubert,^† Maria V. Di Giandomenico,^† Clara Fillaux,^‡ Christophe Den Auwer,*^‡ Philippe Moisy,^‡ and Christoph Hennig^§

Centre National de la Recherche Scientifique/IN2P3/Paris XI, Institut de Physique Nuclaire, 91406 Orsay Cedex, France, Commissariat l'Energie Atomique/Valrh, DEN/DRCP/SCPS, 30207 Bagnols sur Ceze Cedex, France, and Forschungszentrum Rossendorf, 01314 Dresden, Germany, at Rossendorf Beam Line/European Synchrotron Radiation Facility, 38043 Grenoble, France

Inorg. Chem., 2005, 44 (25), pp 9542–9546

DOI: 10.1021/ic0512330

Publication Date (Web): November 8, 2005

†

Institut de Physique Nucléaire.

‡

Commissariat à l'Energie Atomique/Valrhô, DEN/DRCP/SCPS.

To whom correspondence should be addressed. E-mail: christophe.denauwer@cea.fr.

Forschungszentrum Rossendorf, 01314 Dresden, Germany, at Rossendorf Beam Lin/ESRF.

Abstract

The present work describes the first structural studies of protactinium(V) in sulfuric and hydrofluoric acid media using X-ray absorption spectroscopy. The results show unambiguously the absence of the trans-dioxo bond that characterizes the other early actinide elements such as U and Np. In concentrated sulfuric acid (13 M), Pa(V) is proved to exhibit a single oxo bond as postulated in the literature for species in more dilute media. In a 0.5 M HF medium, XANES and EXAFS spectra indicate the absence of any oxo bond: Pa(V) exists in the form of a pure fluoro complex.

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