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dc.contributor.authorBoronski, Josef T; orcid: 0000-0002-1435-6337
dc.contributor.authorWooles, Ashley J; orcid: 0000-0001-7411-9627
dc.contributor.authorLiddle, Stephen T; orcid: 0000-0001-9911-8778
dc.date.accessioned2021-07-09T01:07:50Z
dc.date.available2021-07-09T01:07:50Z
dc.date.issued2020-06-10
dc.identifierhttps://chesterrep.openrepository.com/bitstream/handle/10034/625194/article.pdf?sequence=2
dc.identifier.citationChemical science, volume 11, issue 26, page 6789-6794
dc.identifier.urihttp://hdl.handle.net/10034/625194
dc.descriptionFrom Europe PMC via Jisc Publications Router
dc.descriptionHistory: ppub 2020-06-01, epub 2020-06-10
dc.descriptionPublication status: Published
dc.descriptionFunder: Engineering and Physical Sciences Research Council; Grant(s): EP/M027015/1, EP/P001386/1
dc.description.abstractDespite the vast array of η <sup><i>n</i></sup> -carbocyclic C<sub>5-8</sub> complexes reported for actinides, cyclobutadienyl (C<sub>4</sub>) remain exceedingly rare, being restricted to six uranium examples. Here, overcoming the inherent challenges of installing highly reducing C<sub>4</sub>-ligands onto actinides when using polar starting materials such as halides, we report that reaction of [Th(η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>)<sub>2</sub>] with [K<sub>2</sub>{C<sub>4</sub>(SiMe<sub>3</sub>)<sub>4</sub>}] gives [{Th(η<sup>4</sup>-C<sub>4</sub>[SiMe<sub>3</sub>]<sub>4</sub>)(μ-η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>)(μ-η<sup>2</sup>-C<sub>8</sub>H<sub>8</sub>)(K[C<sub>6</sub>H<sub>5</sub>Me]<sub>2</sub>)}<sub>2</sub>{K(C<sub>6</sub>H<sub>5</sub>Me)}{K}] (<b>1</b>), a new type of heteroleptic actinocene. Quantum chemical calculations suggest that the thorium ion engages in π- and δ-bonding to the η<sup>4</sup>-cyclobutadienyl and η<sup>8</sup>-cyclooctatetraenyl ligands, respectively. Furthermore, the coordination sphere of this bent thorocene analogue is supplemented by an η<sup>2</sup>-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.
dc.languageeng
dc.rightsLicence for this article: cc by
dc.sourceissn: 2041-6520
dc.sourceessn: 2041-6539
dc.sourcenlmid: 101545951
dc.titleHeteroleptic actinocenes: a thorium(iv)-cyclobutadienyl-cyclooctatetraenyl-di-potassium-cyclooctatetraenyl complex.
dc.typearticle
dc.date.updated2021-07-09T01:07:50Z


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