Jump to main content
Jump to site search

Issue 18, 2018
Previous Article Next Article

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

Author affiliations

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. Herein, we report the syntheses of Th–Al bimetallics from reactions between a di-tert-butylcyclopentadienyl supported Th(IV) dihalide (Cp2ThCl2) 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 [Cp2Th(μ-H3)AlC(SiMe3)3 (4)]. The U(III) analogue [Cp2U(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.

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

Back to tab navigation

Supplementary files

Article information


Submitted
17 Mar 2018
Accepted
13 Apr 2018
First published
24 Apr 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 4317-4324
Article type
Edge Article

Chemical structure and bonding in a thorium(III)–aluminum heterobimetallic complex

A. B. Altman, A. C. Brown, G. Rao, T. D. Lohrey, R. D. Britt, L. Maron, S. G. Minasian, D. K. Shuh and J. Arnold, Chem. Sci., 2018, 9, 4317
DOI: 10.1039/C8SC01260A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements