Nucleophilic aromatic substitution of Bis(pentafluorophenyl)mercury with various bulky nucleophiles and the structures of [Hg(C₆F₄X-4)₂)] (X = cyclo-C₅H₁₀N, OCH(CH₃)₂, OC(CH₃)₃)

Deacon, Glen B.;Junk, Peter C.;Luu, Jenny

Abstract

Reactions of bis(pentafluorophenyl)mercury with piperidine, sodium iso-propoxide or sodium tert-butoxide have yielded the corresponding 4-substituted tetrafluorophenylmercurials, [Hg(C₆F₄X-4)₂] (X = cyclo-C₅H₁₀N (1), OCH(CH₃)₂ (2), OC(CH₃)₃)(3) in reasonable yields but the bulkier nucleophiles, cis-2,6-dimethylpiperidine and 2,6-di-iso-propylphenolate (from sodium 2,6-di-iso-propylphenolate) decomposed the mercurial into pentafluorobenzene. Treatment of bis(pentafluorophenyl) mercury with another bulky nucleophile, 2,6-diphenylphenolate (from sodium 2,6-diphenylphenolate), in methanol, resulted in the unexpected formation of [Hg(C₆F₄(OMe)-4)₂] (4). The structures of all the mercurials have linear C-Hg-C stereochemistry with two coplanar aryl rings. Amongst a complex series of supramolecular interactions, Hg center dot center dot center dot O bonding is observed for the alkoxy substituted mercurials but there are no Hg center dot center dot center dot N interactions in the structure of bis(2,3,5,6-tetrafluoro-4-piperidinophenyl) mercury.

Journal

Australian Journal of Chemistry

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1445-0038

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CSIRO Publishing

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DOI

10.1071/CH13227