| Title: |
Unusual structure, bonding and properties in a californium borate |
| Authors: |
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. |
| Contributors: |
Department of Chemistry and Biochemistry; Florida State University Tallahassee (FSU); Department of Chemistry; University of Alabama Tuscaloosa (UA); Department of Chemistry, Supercomputing Institute, and Chemical Theory Center; University of Minnesota Twin Cities (UMN); University of Minnesota System (UMN)-University of Minnesota System (UMN); Laboratoire de physique subatomique et des technologies associées (SUBATECH); Mines Nantes (Mines Nantes)-Université de Nantes (UN)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS); Institute for Energy and Climate Research - Nuclear Waste Management and Reactor Safety (IEK-6); Forschungszentrum Jülich GmbH; Helmholtz-Gemeinschaft = Helmholtz Association-Helmholtz-Gemeinschaft = Helmholtz Association; Institut für Kristallographie; RWTH Aachen University = Rheinisch-Westfälische Technische Hochschule Aachen (RWTH Aachen); Nuclear Materials Processing Group Oak Ridge; Oak Ridge National Laboratory Oak Ridge (ORNL); UT-Battelle, LLC-UT-Battelle, LLC; Institut für Geowissenschaften Kiel; Christian-Albrechts-Universität zu Kiel = Christian-Albrechts University of Kiel = Université Christian-Albrechts de Kiel (CAU); Argonne National Laboratory Lemont (ANL) |
| Source: |
ISSN: 1755-4330 ; Nature Chemistry ; https://in2p3.hal.science/in2p3-00966875 ; Nature Chemistry, 2014, 6, pp.387-392. ⟨10.1038/nchem.1896⟩. |
| Publisher Information: |
CCSD; Nature Publishing Group |
| Publication Year: |
2014 |
| Collection: |
Université de Nantes: HAL-UNIV-NANTES |
| Subject Terms: |
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry |
| Description: |
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. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1038/nchem.1896 |
| Availability: |
https://in2p3.hal.science/in2p3-00966875; https://in2p3.hal.science/in2p3-00966875v1/document; https://in2p3.hal.science/in2p3-00966875v1/file/manfinalversionPUBLISHED.pdf; https://doi.org/10.1038/nchem.1896 |
| Rights: |
info:eu-repo/semantics/OpenAccess |
| Accession Number: |
edsbas.FAC44F1C |
| Database: |
BASE |