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

doi:10.1038/nchem.1896

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

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113 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 language	English
Pages (from-to)	387-392
Number of pages	6
Journal	Nature Chemistry
Volume	6
Issue number	5
DOIs	https://doi.org/10.1038/nchem.1896
State	Published - May 2014

Funding

We are grateful for support provided by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, Heavy Elements Chemistry Program, US Department of Energy under Grants DE-SC0002215, DE-FG02-13ER16414, DE-SC002183 (N.P., R.M. and L.G.), and DE-AC02-06CH11357 (D.A.D., G.L. and L.S.), and for support from the National Science Foundation CAREER award DMR-0955353 (M.S.). Collaborative work is supported via the Helmholtz Association, Grant Number VH-NG-815. The 249Cf was provided to Florida State University via the Isotope Development and Production for Research and Applications Program through the Radiochemical Engineering and Development Center at ORNL and was purchased via the Gregory R. Choppin Chair Endowment.

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Polinski, M. J., Garner, E. B., Maurice, R., Planas, N., Stritzinger, J. T., Parker, T. G., Cross, J. N., Green, T. D., Alekseev, E. V., Van Cleve, S. M., Depmeier, W., Gagliardi, L., Shatruk, M., Knappenberger, K. L., Liu, G., Skanthakumar, S., Soderholm, L., Dixon, D. A., & 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

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title = "Unusual structure, bonding and properties in a californium borate",

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.",

author = "Polinski, {Matthew J.} and Garner, {Edward B.} and R{\'e}mi Maurice and Nora Planas and Stritzinger, {Jared T.} and Parker, {T. Gannon} and Cross, {Justin N.} and Green, {Thomas D.} and Alekseev, {Evgeny V.} and {Van Cleve}, {Shelley M.} and Wulf Depmeier and Laura Gagliardi and Michael Shatruk and Knappenberger, {Kenneth L.} and Guokui Liu and S. Skanthakumar and Lynda Soderholm and Dixon, {David A.} and Albrecht-Schmitt, {Thomas E.}",

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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

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AU - Garner, Edward B.

AU - Maurice, Rémi

AU - Planas, Nora

AU - Stritzinger, Jared T.

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.

PY - 2014/5

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N2 - 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.

AB - 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.

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Unusual structure, bonding and properties in a californium borate

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