Unusual structure, bonding and properties in a californium borate.

Autor: Polinski MJ; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Garner EB 3rd; Department of Chemistry, The University of Alabama, Shelby Hall, Tuscaloosa Alabama 35487, USA., Maurice R; 1] Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA [2] SUBATECH, Unité Mixte de Recherche 6457, Centre National de la Recherche Scientifique, Institut National de Physique Nucléaire et de Physique des Particules, Ecole des Mines de Nantes, Université de Nantes, 4 rue Alfred Kastler, BP20722, 44307 Nantes Cédex 3, France., Planas N; Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA., Stritzinger JT; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Parker TG; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Cross JN; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Green TD; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Alekseev EV; 1] Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, 52428 Jülich, Germany [2] Institut für Kristallographie, Rheinisch-Westfaelische Technische Hochschule Aachen University, 52066 Aachen, Germany., Van Cleve SM; Nuclear Materials Processing Group, Oak Ridge National Laboratory, One Bethel Valley Rd, Oak Ridge, Tennessee 37830, USA., Depmeier W; Institut für Geowissenschaften, Universität Kiel, 24118 Kiel, Germany., Gagliardi L; Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA., Shatruk M; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Knappenberger KL; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA., Liu G; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA., Skanthakumar S; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA., Soderholm L; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA., Dixon DA; Department of Chemistry, The University of Alabama, Shelby Hall, Tuscaloosa Alabama 35487, USA., Albrecht-Schmitt TE; Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2014 May; Vol. 6 (5), pp. 387-92. Date of Electronic Publication: 2014 Mar 23.
DOI: 10.1038/nchem.1896
Abstrakt: 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.
Databáze: MEDLINE