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    Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations

    Coughlin, Omar and Krämer, Tobias and Benjamin, Sophie L. (2020) Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations. Dalton Transactions, 49 (6). pp. 1726-1730. ISSN 1477-9226

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    The pentamethylcyclopentadienyl (Cp*) antimony(III) cations [Cp*2Sb][B(C6F5)4], [Cp2*Sb][OTf], [Cp*SbCl][B(C6F5)4] and [Cp*Sb][OTf]2 have been isolated and structurally characterised. [Cp*SbCl]+ forms dimers in the solid state via an intermolecular Sb–Cl interaction. Initial screening shows that [Cp*SbCl][B(C6F5)4] is significantly Lewis acidic and can catalyse the dimerisation of 1,1-diphenylethylene; [Cp2*Sb][B(C6F5)4] exhibits negligible Lewis acidity. Highly unstable [Cp*SbF][B(C6F5)4] could not be isolated, but stabilisation with the IMes ligand allowed isolation of [Cp*SbF(IMes)][B(C6F5)4]. Fluorodechlorination of CH2Cl2 and PhCCl3 was observed in the presence of crude [Cp*SbF][B(C6F5)4] in solution. A computational mechanistic investigation suggests that the latter proceeds via a carbocation intermediate.

    Item Type: Article
    Keywords: Diverse structure; reactivity; pentamethylcyclopentadienyl; antimony(iii); cations;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Faculty of Science and Engineering > Research Institutes > Hamilton Institute
    Item ID: 15536
    Identification Number:
    Depositing User: Tobias Kraemer
    Date Deposited: 21 Feb 2022 16:30
    Journal or Publication Title: Dalton Transactions
    Publisher: Royal Society of Chemistry
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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