Unusual structure, bonding and properties in a californium borate

Polinski, Matthew J., Garner, Edward B., Maurice, Remi, Planas, Nora, Stritzinger, Jared T., Parker, T. Gannon, Cross, Justin N., Green, Thomas D., Alekseev, Evgeny V., Van Cleve, Shelley M., Depmeier, Wulf, Gagliardi, Laura, Shatruk, Michael, Knappenberger, Kenneth L., Liu, Guokui, Skanthakumar, S., Soderholm, Lynda, Dixon, David A. and Albrecht-Schmitt, Thomas E. (2014) Unusual structure, bonding and properties in a californium borate Nature Chemistry, 6 (5). pp. 387-392.

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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.

Document Type: Article
Additional Information: Times Cited: 4 0 4
Research affiliation: OceanRep > The Future Ocean - Cluster of Excellence
Kiel University
Refereed: Yes
ISSN: 1755-4330
Projects: Future Ocean
Date Deposited: 30 Mar 2015 12:40
Last Modified: 28 Mar 2018 10:28
URI: http://eprints.uni-kiel.de/id/eprint/28146

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