A new divalent organoeuropium(II) fluoride and serendipitous discovery of an alkoxide complex from pentaphenylcyclopentadiene precursors
Journal Publication ResearchOnline@JCUAbstract
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.
Journal
Australian Journal of Chemistry
Publication Name
Australian Journal of Chemistry
Volume
75
ISBN/ISSN
1445-0038
Edition
N/A
Issue
8 & 9
Pages Count
8
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N/A
Publisher
CSIRO Publishing
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Date
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EISSN
N/A
DOI
10.1071/CH21324