Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations

Coughlin, O ORCID: https://orcid.org/0000-0003-4528-9787, Krämer, T and Benjamin, SL ORCID: https://orcid.org/0000-0002-5038-1599, 2020. Diverse structure and reactivity of pentamethylcyclopentadienyl antimony(iii) cations. Dalton Transactions. ISSN 1477-9226

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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.

Item Type:	Journal article
Publication Title:	Dalton Transactions
Creators:	Coughlin, O., Krämer, T. and Benjamin, S.L.
Publisher:	Royal Society of Chemistry
Date:	19 January 2020
ISSN:	1477-9226
Identifiers:	Number Type 10.1039/d0dt00024h DOI 1275199 Other
Divisions:	Schools > School of Science and Technology
Record created by:	Linda Sullivan
Date Added:	22 Jan 2020 11:24
Last Modified:	31 May 2021 15:07
URI:	https://irep.ntu.ac.uk/id/eprint/39045

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