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Issue 26, 2020
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Heteroleptic actinocenes: a thorium(iv)–cyclobutadienyl–cyclooctatetraenyl–di-potassium-cyclooctatetraenyl complex

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Abstract

Despite the vast array of ηn-carbocyclic C5–8 complexes reported for actinides, cyclobutadienyl (C4) remain exceedingly rare, being restricted to six uranium examples. Here, overcoming the inherent challenges of installing highly reducing C4-ligands onto actinides when using polar starting materials such as halides, we report that reaction of [Th(η8-C8H8)2] with [K2{C4(SiMe3)4}] gives [{Th(η4-C4[SiMe3]4)(μ-η8-C8H8)(μ-η2-C8H8)(K[C6H5Me]2)}2{K(C6H5Me)}{K}] (1), a new type of heteroleptic actinocene. Quantum chemical calculations suggest that the thorium ion engages in π- and δ-bonding to the η4-cyclobutadienyl and η8-cyclooctatetraenyl ligands, respectively. Furthermore, the coordination sphere of this bent thorocene analogue is supplemented by an η2-cyclooctatetraenyl interaction, which calculations suggest is composed of σ- and π-symmetry donations from in-plane in- and out-of-phase C[double bond, length as m-dash]C 2p-orbital combinations to vacant thorium 6d orbitals. The characterisation data are consistent with this being a metal–alkene-type interaction that is integral to the bent structure and stability of this complex.

Graphical abstract: Heteroleptic actinocenes: a thorium(iv)–cyclobutadienyl–cyclooctatetraenyl–di-potassium-cyclooctatetraenyl complex

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Supplementary files

Article information


Submitted
01 May 2020
Accepted
10 Jun 2020
First published
10 Jun 2020

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

Chem. Sci., 2020,11, 6789-6794
Article type
Edge Article

Heteroleptic actinocenes: a thorium(IV)–cyclobutadienyl–cyclooctatetraenyl–di-potassium-cyclooctatetraenyl complex

J. T. Boronski, A. J. Wooles and S. T. Liddle, Chem. Sci., 2020, 11, 6789
DOI: 10.1039/D0SC02479A

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