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Title: Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex

Abstract

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. Here in this paper, we report the syntheses of Th–Al bimetallics from reactions between a di-tert-butylcyclopentadienyl supported Th(IV) dihalide (Cp‡ 2ThCl 2) and an anionic aluminum hydride salt [K(H 3AlC(SiMe 3) 3)]. Reduction of the [Th(IV)](Cl)–[Al] product resulted in a [Th(III)]–[Al] complex [Cp‡ 2Th(μ-H 3)AlC(SiMe 3) 3]. The U(III) analogue [Cp‡ 2U(μ-H 3)AlC(SiMe 3) 3] 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 frommore » 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.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Univ. of California, Davis, CA (United States). Dept. of Chemistry
  4. Univ. de Toulouse, Toulouse (France). Laboratoire de Physique et Chimie de Nano-Objets (LPCNO)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1434399
Alternate Identifier(s):
OSTI ID: 1461125
Grant/Contract Number:  
AC02-05CH11231; NA0003180; NA0000979
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 18; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Altman, Alison B., Brown, Alexandra C., Rao, Guodong, Lohrey, Trevor D., Britt, R. David, Maron, Laurent, Minasian, Stefan G., Shuh, David K., and Arnold, John. Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex. United States: N. p., 2018. Web. doi:10.1039/c8sc01260a.
Altman, Alison B., Brown, Alexandra C., Rao, Guodong, Lohrey, Trevor D., Britt, R. David, Maron, Laurent, Minasian, Stefan G., Shuh, David K., & Arnold, John. Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex. United States. doi:10.1039/c8sc01260a.
Altman, Alison B., Brown, Alexandra C., Rao, Guodong, Lohrey, Trevor D., Britt, R. David, Maron, Laurent, Minasian, Stefan G., Shuh, David K., and Arnold, John. Mon . "Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex". United States. doi:10.1039/c8sc01260a.
@article{osti_1434399,
title = {Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex},
author = {Altman, Alison B. and Brown, Alexandra C. and Rao, Guodong and Lohrey, Trevor D. and Britt, R. David and Maron, Laurent and Minasian, Stefan G. and Shuh, David K. and Arnold, John},
abstractNote = {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. Here in this paper, 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)]. Reduction of the [Th(IV)](Cl)–[Al] product resulted in a [Th(III)]–[Al] complex [Cp‡2Th(μ-H3)AlC(SiMe3)3]. The U(III) analogue [Cp‡2U(μ-H3)AlC(SiMe3)3] 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.},
doi = {10.1039/c8sc01260a},
journal = {Chemical Science},
issn = {2041-6520},
number = 18,
volume = 9,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c8sc01260a

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Cited by: 4 works
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Figures / Tables:

Scheme 1 Scheme 1: Synthesis of 2 and 3.

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    Works referencing / citing this record:

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    journal, March 2010

    • Daly, Scott R.; Piccoli, Paula M. B.; Schultz, Arthur J.
    • Angewandte Chemie International Edition, Vol. 49, Issue 19
    • DOI: 10.1002/anie.200905797

    Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes
    journal, February 2014

    • Ward, Ashleigh L.; Lukens, Wayne W.; Lu, Connie C.
    • Journal of the American Chemical Society, Vol. 136, Issue 9
    • DOI: 10.1021/ja413192m

    Expanding the chemistry of U3+ reducing agents
    journal, April 2006


    Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
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    • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
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    • DOI: 10.1021/ja9015759

    A Linear, O-Coordinated  1-CO2 Bound to Uranium
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    The vitality of uranium molecular chemistry at the dawn of the XXIst century
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    • Angewandte Chemie International Edition in English, Vol. 32, Issue 10
    • DOI: 10.1002/anie.199314281

    Expanding Thorium Hydride Chemistry Through Th 2+ , Including the Synthesis of a Mixed-Valent Th 4+ /Th 3+ Hydride Complex
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    • DOI: 10.1038/nchem.1028

    Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding
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    • DOI: 10.1002/anie.201402050

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    Probing the Coordinative Unsaturation and Local Environment of Ti 3+  Sites in an Activated High-Yield Ziegler-Natta Catalyst
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    • DOI: 10.1002/anie.201412052

    Evidence for the Involvement of 5f Orbitals in the Bonding and Reactivity of Organometallic Actinide Compounds: Thorium(IV) and Uranium(IV) Bis(hydrazonato) Complexes
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.