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)

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

doi:10.1071/CH13227

RESEARCH ARTICLE

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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)

Glen B. Deacon ^A ^C , Peter C. Junk ^B ^C and Jenny Luu ^A

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.

^B School of Pharmacy and Molecular Sciences, James Cook University, Townsville, Qld 4811, Australia.

^C Corresponding authors. Email: glen.deacon@monash.edu; peter.junk@jcu.edu.au

Australian Journal of Chemistry 66(10) 1253-1259 https://doi.org/10.1071/CH13227
Submitted: 1 May 2013 Accepted: 18 June 2013 Published: 30 July 2013

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⋯O bonding is observed for the alkoxy substituted mercurials but there are no Hg⋯N interactions in the structure of bis(2,3,5,6-tetrafluoro-4-piperidinophenyl)mercury.

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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)

Abstract

References

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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)