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.

doi:10.1038/nchem.1896

Unusual structure, bonding and properties in a californium borate

Journal Article · Sun Mar 23 00:00:00 EDT 2014 · Nature Chemistry

DOI:https://doi.org/10.1038/nchem.1896· OSTI ID:1393977

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.

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.

Research Organization:: Argonne National Laboratory (ANL)

Sponsoring Organization:: USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1393977

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 5 Vol. 6; ISSN 1755-4330

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

References (37)

A simple measure of electron localization in atomic and molecular systems Becke, A. D.; Edgecombe, K. E. The Journal of Chemical Physics, Vol. 92, Issue 9 https://doi.org/10.1063/1.458517	journal	May 1990
MOLCAS 7: The Next Generation Aquilante, Francesco; De Vico, Luca; FerrÃ©, Nicolas Journal of Computational Chemistry, Vol. 31, Issue 1 https://doi.org/10.1002/jcc.21318	journal	January 2010
Stereochemistry of Compounds with Coordination Number Ten Ruiz-Martínez, Antonio; Alvarez, Santiago Chemistry - A European Journal, Vol. 15, Issue 30 https://doi.org/10.1002/chem.200900547	journal	July 2009
Quantum electrodynamical corrections to the fine structure of helium Douglas, Marvin; Kroll, Norman M. Annals of Physics, Vol. 82, Issue 1 https://doi.org/10.1016/0003-4916(74)90333-9	journal	January 1974
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Segmented contraction scheme for small-core actinide pseudopotential basis sets Cao, Xiaoyan; Dolg, Michael Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3 https://doi.org/10.1016/j.theochem.2003.12.015	journal	March 2004
The Curium Aqua Ion Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E. Inorganic Chemistry, Vol. 46, Issue 9 https://doi.org/10.1021/ic061798b	journal	April 2007
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Classification of chemical bonds based on topological analysis of electron localization functions Silvi, B.; Savin, A. Nature, Vol. 371, Issue 6499 https://doi.org/10.1038/371683a0	journal	October 1994
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Uranium Tris-aryloxide Derivatives Supported by Triazacyclononane: Engendering a Reactive Uranium(III) Center with a Single Pocket for Reactivity Castro-Rodriguez, Ingrid; Olsen, Kristian; Gantzel, Peter Journal of the American Chemical Society, Vol. 125, Issue 15 https://doi.org/10.1021/ja028342n	journal	April 2003
Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements Laubereau, Peter G.; Burns, John H. Inorganic Chemistry, Vol. 9, Issue 5 https://doi.org/10.1021/ic50087a018	journal	May 1970
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
Valence determination as a function of doping in PrBa 2 Cu 3 O 7 Staub, U.; Soderholm, L.; Wasserman, S. R. Physical Review B, Vol. 61, Issue 2 https://doi.org/10.1103/PhysRevB.61.1548	journal	January 2000
Hexagonal and orthorhombic crystal structures of californium trichloride Burns, J. H.; Peterson, J. R.; Baybarz, R. D. Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 4 https://doi.org/10.1016/0022-1902(73)80189-7	journal	April 1973
[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola Angewandte Chemie International Edition, Vol. 49, Issue 36 https://doi.org/10.1002/anie.201001077	journal	June 2010
Accurate relativistic Gaussian basis sets for H through Lr determined by atomic self-consistent field calculations with the third-order Douglas–Kroll approximation Tsuchiya, Takashi; Abe, Minori; Nakajima, Takahito The Journal of Chemical Physics, Vol. 115, Issue 10 https://doi.org/10.1063/1.1390515	journal	September 2001
Polyhedral Structures with an Odd Number of Vertices: Nine-Coordinate Metal Compounds Ruiz-Martínez, Antonio; Casanova, David; Alvarez, Santiago Chemistry - A European Journal, Vol. 14, Issue 4 https://doi.org/10.1002/chem.200701137	journal	January 2008
Spectroscopy and structure of selected lanthanide polymeric and monomeric systems Legendziewicz, Janina Journal of Alloys and Compounds, Vol. 300-301 https://doi.org/10.1016/S0925-8388(99)00735-5	journal	April 2000
Spectroscopy and structure of selected lanthanide polymeric and monomeric systems Legendziewicz, Janina Journal of Alloys and Compounds, Vol. 300-301 https://doi.org/10.1016/s0925-8388(99)00735-5	journal	April 2000
The Structures and Optical Spectra of Hydrated Transplutonium Ions in the Solid State and in Solution Lindqvist-Reis, Patric; Apostolidis, Christos; Rebizant, Jean Angewandte Chemie International Edition, Vol. 46, Issue 6 https://doi.org/10.1002/anie.200603947	journal	January 2007
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Single-crystal structure validation with the program PLATON Spek, A. L. Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13 https://doi.org/10.1107/S0021889802022112	journal	January 2003
First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination. Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. ChemInform, Vol. 37, Issue 15 https://doi.org/10.1002/chin.200615001	journal	April 2006
ChemInform Abstract: Does Covalency Increase or Decrease Across the Actinide Series? Implications for Minor Actinide Partitioning. Kaltsoyannis, Nikolas ChemInform, Vol. 44, Issue 20 https://doi.org/10.1002/chin.201320227	journal	April 2013
A theoretical calculation of vibronic coupling strength: the trend in the lanthanide ion series and the host-lattice dependence Campos, A. F.; Meijerink, A.; Donegá, C. de Mello Journal of Physics and Chemistry of Solids, Vol. 61, Issue 9 https://doi.org/10.1016/S0022-3697(00)00007-X	journal	September 2000
Differentiating between Trivalent Lanthanides and Actinides Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja303804r	journal	June 2012
First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic051667v	journal	January 2006
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe Angewandte Chemie International Edition, Vol. 49, Issue 22 https://doi.org/10.1002/anie.200906129	journal	April 2010
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators Hess, Bernd A. Physical Review A, Vol. 33, Issue 6 https://doi.org/10.1103/PhysRevA.33.3742	journal	June 1986
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank Chemical Reviews, Vol. 88, Issue 6 https://doi.org/10.1021/cr00088a005	journal	September 1988
Atomic shell structure and electron numbers Kohout, M.; Savin, A. International Journal of Quantum Chemistry, Vol. 60, Issue 4 https://doi.org/10.1002/(SICI)1097-461X(1996)60:4<875::AID-QUA10>3.0.CO;2-4	journal	November 1996
Magnetic properties of Dy in Pb2Sr2DyCu3O8 Skanthakumar, S.; Soderholm, L.; Movshovich, R. Journal of Alloys and Compounds, Vol. 303-304 https://doi.org/10.1016/S0925-8388(00)00589-2	journal	May 2000
Synthesis of Rare Earth Polyborates Using Molten Boric Acid as a Flux Li, Linyan; Lu, Peichao; Wang, Yaoyang Chemistry of Materials, Vol. 14, Issue 12 https://doi.org/10.1021/cm0203870	journal	December 2002
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/physrevb.46.6671	journal	September 1992

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Emergence of californium as the second transitional element in the actinide series Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7827	journal	April 2015

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