Unusual structure, bonding and properties in a californium borate

Matthew J. Polinski, Edward B. Garner, Rémi Maurice, Nora Planas, Jared T. Stritzinger, T. Gannon Parker, Justin N. Cross, Thomas D. Green, Evgeny V. Alekseev, Shelley M. Van Cleve, Wulf Depmeier, Laura Gagliardi, Michael Shatruk, Kenneth L. Knappenberger, Guokui Liu, S. Skanthakumar, Lynda Soderholm, David A. Dixon, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticlepeer-review

72 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)387-392
Number of pages6
JournalNature Chemistry
Volume6
Issue number5
DOIs
StatePublished - May 2014

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

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