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Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations

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Abstract

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.

Graphical abstract: Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations

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Article information


Submitted
03 Jan 2020
Accepted
09 Jan 2020
First published
13 Jan 2020

Dalton Trans., 2020, Advance Article
Article type
Communication

Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(III) cations

O. Coughlin, T. Krämer and S. L. Benjamin, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT00024H

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