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

Chemical Science
Alison B AltmanJohn Arnold

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 (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 th...Continue Reading

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Citations

Jun 12, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J Inman, F Geoffrey N Cloke
Oct 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Justin C WedalWilliam J Evans
Oct 13, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A Boreen, John Arnold
Mar 21, 2019·Journal of the American Chemical Society·Michael A BoreenJohn Arnold
Jul 25, 2019·Journal of the American Chemical Society·Daniel N HuhWilliam J Evans
Dec 1, 2018·Journal of the American Chemical Society·Martin RahmRoald Hoffmann
Oct 24, 2020·Inorganic Chemistry·Robert J WardJustin R Walensky
Aug 28, 2021·Chemical Reviews·Matthew M D RoyEric Rivard
Nov 18, 2021·Journal of the American Chemical Society·Mark D StraubJohn Arnold

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Methods Mentioned

BETA
X-ray
NMR

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