1. Chemical structure and bonding in a thorium(<scp>iii</scp>)–aluminum heterobimetallic complex
- Author
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Laurent Maron, Stefan G. Minasian, R. David Britt, Alexandra C. Brown, David K. Shuh, John Arnold, Alison B. Altman, Trevor D. Lohrey, Guodong Rao, Department of Chemistry [Berkeley], University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Earth Sciences Division (ESD), Lawrence Berkeley National Lab, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences Heavy Element Chemistry Program of the U.S. Department of Energy (DOE) at LBNL [DE-AC02-05CH11231], NIH [1R35GM126961-01], Department of Energy National Nuclear Security Administration through the Nuclear Science and Security Consortium [DE-NA0003180, DE-NA0000979], U.S. DOE Office of Science User Facility [DE-AC02-05CH11231], DOE Integrated University Program Fellowships at the University of California, Berkeley, and Goldwater Foundation
- Subjects
010405 organic chemistry ,Chemistry ,General Chemistry ,Electronic structure ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,3. Good health ,law.invention ,Delocalized electron ,Crystallography ,Unpaired electron ,Transition metal ,law ,Chemical Sciences ,Molecule ,Density functional theory ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Electron paramagnetic resonance ,Valence electron - Abstract
We describe the syntheses of [Th(iii)]–[Al] and [U(iii)]–[Al] bimetallics that demonstrate An→Al interactions where the actinide behaves as an electron donor., Thorium sits at a unique position on the periodic table. On one hand, there is little evidence that its 5f orbitals engage in bonding as they do in other early actinides; on the other hand, its chemistry is distinct from Lewis acidic transition metals. To gain insight into the underlying electronic structure of Th and develop trends across the actinide series, it is useful to study Th(iii) and Th(ii) systems with valence electrons that may engage in non-electrostatic metal–ligand interactions, although only a handful of such systems are known. To expand the range of low-valent compounds and gain deeper insight into Th electronic structure, we targeted actinide bimetallic complexes containing metal–metal bonds. Herein, we report the syntheses of Th–Al bimetallics from reactions between a di-tert-butylcyclopentadienyl supported Th(iv) dihalide (Cp‡2ThCl2) and an anionic aluminum hydride salt [K(H3AlC(SiMe3)3) (1)]. Reduction of the [Th(iv)](Cl)–[Al] product resulted in a [Th(iii)]–[Al] complex [Cp‡2Th(μ-H3)AlC(SiMe3)3 (4)]. The U(iii) analogue [Cp‡2U(μ-H3)AlC(SiMe3)3 (5)] could be synthesized directly from a U(iii) halide starting material. Electron paramagnetic resonance studies on 4 demonstrate hyperfine interactions between the unpaired electron and the Al atom indicative of spin density delocalization from the Th metal center to the Al. Density functional theory and atom in molecules calculations confirmed the presence of An→Al interactions in 4 and 5, which represents the first examples of An→M interactions where the actinide behaves as an electron donor.
- Published
- 2018
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