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 journalArticle

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 - Jan 1 2014

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Californium
Borates
Actinoid Series Elements
Actinides
Lanthanoid Series Elements
Rare earth elements
Ligands
Complexation
Crystals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Polinski, M. J., Garner, E. B., Maurice, R., Planas, N., Stritzinger, J. T., Parker, T. G., ... Albrecht-Schmitt, T. E. (2014). Unusual structure, bonding and properties in a californium borate. Nature Chemistry, 6(5), 387-392. https://doi.org/10.1038/nchem.1896
Polinski, Matthew J. ; Garner, Edward B. ; Maurice, Rémi ; 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. ; Albrecht-Schmitt, Thomas E. / Unusual structure, bonding and properties in a californium borate. In: Nature Chemistry. 2014 ; Vol. 6, No. 5. pp. 387-392.
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Polinski, MJ, Garner, EB, Maurice, R, Planas, N, Stritzinger, JT, Parker, TG, Cross, JN, Green, TD, Alekseev, EV, Van Cleve, SM, Depmeier, W, Gagliardi, L, Shatruk, M, Knappenberger, KL, Liu, G, Skanthakumar, S, Soderholm, L, Dixon, DA & Albrecht-Schmitt, TE 2014, 'Unusual structure, bonding and properties in a californium borate.', Nature Chemistry, vol. 6, no. 5, pp. 387-392. https://doi.org/10.1038/nchem.1896

Unusual structure, bonding and properties in a californium borate. / Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi; 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.; Albrecht-Schmitt, Thomas E.

In: Nature Chemistry, Vol. 6, No. 5, 01.01.2014, p. 387-392.

Research output: Contribution to journalArticle

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AU - Maurice, Rémi

AU - Planas, Nora

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AU - Parker, T. Gannon

AU - Cross, Justin N.

AU - Green, Thomas D.

AU - Alekseev, Evgeny V.

AU - Van Cleve, Shelley M.

AU - Depmeier, Wulf

AU - Gagliardi, Laura

AU - Shatruk, Michael

AU - Knappenberger, Kenneth L.

AU - Liu, Guokui

AU - Skanthakumar, S.

AU - Soderholm, Lynda

AU - Dixon, David A.

AU - Albrecht-Schmitt, Thomas E.

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Polinski MJ, Garner EB, Maurice R, Planas N, Stritzinger JT, Parker TG et al. Unusual structure, bonding and properties in a californium borate. Nature Chemistry. 2014 Jan 1;6(5):387-392. https://doi.org/10.1038/nchem.1896