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

Chemistry

Research output: Contribution to journal › Article › peer-review

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 (US)
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 - Jan 1 2014

All Science Journal Classification (ASJC) codes

General Chemistry
General Chemical Engineering

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10.1038/nchem.1896

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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

@article{f4300fac18564435b06d23828159c68e,

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.}",

year = "2014",

month = jan,

day = "1",

doi = "10.1038/nchem.1896",

language = "English (US)",

volume = "6",

pages = "387--392",

journal = "Nature Chemistry",

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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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T1 - Unusual structure, bonding and properties in a californium borate.

AU - Polinski, Matthew J.

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 - 2014/1/1

Y1 - 2014/1/1

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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JF - Nature Chemistry

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Unusual structure, bonding and properties in a californium borate.

Abstract

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