This title appears in the Scientific Report : 2014 

Unusual structure, bonding and properties in a californium borate
Polinski, Matthew J. (Corresponding Author)
Garner, Edward B. / Maurice, Rémi / Planas, Nora / Stritzinger, Jared T. / Parker, T. Gannon / Cross, Justin N. / Green, Thomas D. / Alekseev, Evgeny / Van Cleve, Shelley M. / Depmeier, Wulf / Gagliardi, Laura / Shatruk, Michael / Knappenberger, Kenneth L. / Liu, Guokui / Skanthakumar, S. / Soderholm, Lynda / Dixon, David A. / Albrecht-Schmitt, Thomas E.
Nukleare Entsorgung und Reaktorsicherheit; IEK-6
Nature chemistry, 6 (2014) 5, S. 387 - 392
London Nature Publishing Group 2014
24755589
10.1038/nchem.1896
Journal Article
Helmholtz Young Investigators Group: Energy
Safety Research for Nuclear Waste Disposal
Please use the identifier: http://dx.doi.org/10.1038/nchem.1896 in citations.
The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.