A new divalent organoeuropium(II) fluoride and serendipitous discovery of an alkoxide complex from pentaphenylcyclopentadiene precursors
Shephard, Angus C.G., Delon, Aymeric, Kelly, Rory P., Guo, Zhifang, Chevreux, Sylviane, Lemercier, Gilles, Deacon, Glen B., Dushenko, Galina A., Jaroschik, Florian, and Junk, Peter C. (2022) A new divalent organoeuropium(II) fluoride and serendipitous discovery of an alkoxide complex from pentaphenylcyclopentadiene precursors. Australian Journal of Chemistry, 75 (8 & 9). pp. 746-753.
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Abstract
From the redox-transmetallation protolysis (RTP) reaction of europium metal, Hg(C₆F₅)₂ and pentaphenylcyclopentadiene, we isolated and crystallographically characterised small amounts of the first divalent europium fluoride half-sandwich complex [Eu(C₅Ph₅)(μ-F)(thf)₂]₂ (1). Subsequently, a rational synthesis of this complex from in situ formed [EuF₂(thf)n] and [Eu(C₅Ph₅)₂] was carried out. In addition, the new divalent Eu alkoxide complex [Eu(OC₅Ph₅∗)₂(thf)₄] (2) (OC₅Ph₅∗ = 2,3,4,5,5 pentaphenylcyclopenta-1,3-dienolate) was identified by X-ray diffraction analysis, in which an intriguing phenyl group migration in the cyclopentadiene ligand occurred. This complex was shown to be derived from small impurities of 1,2,3,4,5-pentaphenylcyclopenta-1,3-dienol (C₅Ph₅OH) in the C₅Ph₅H starting material and was then synthesised on a larger scale. Density functional theory calculations provided evidence for the facile phenyl group migration observed in the cyclopentadienolate ring.
| Item ID: | 74705 |
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| Item Type: | Article (Research - C1) |
| ISSN: | 1445-0038 |
| Keywords: | 2,3,4,5,5-pentaphenylcyclopenta-1,3-dienolate, bis(pentafluorophenyl)mercury, C-F activation, DFT calculations, Europium metal, pentaphenylcyclopentadiene, redox transmetallation/protolysis |
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| Copyright Information: | © 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND) |
| Funders: | Australian Research Council (ARC) |
| Projects and Grants: | ARC DP190100798 |
| Date Deposited: | 25 Oct 2022 00:49 |
| FoR Codes: | 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 100% |
| SEO Codes: | 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 100% |
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