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Ionization of Gold (gamma-Methoxy)vinyl Complexes Generates Reactive Gold Vinyl Carbene Complexes

Abstract

Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf– {L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P(t-Bu)2o-biphenyl, Ar = Ph, 4-C6H4OMe [(E)-5c]} were generated in solution via Lewis acid-mediated ionization of the corresponding gold (γ-methoxy)vinyl complexes (E)-[(L)AuC(H)C(H)C(OMe)Ar2]+ OTf at or below –95 °C. Complexes (E)-5b and (E)-5c were fully characterized in solution employing multinuclear NMR spectroscopy, which established the predominant contribution of the aurated allylic cation resonance structure. Complex (E)-5b reacted rapidly at –95 °C with neutral two-electron, hydride, and oxygen atom donors exclusively at the C1 position of the vinyl carbene moiety and with p-methoxystyrene to form vinylcyclopropane. In the absence of nucleophile (E)-5a decomposed predominantly via intermolecular carbene dimerization whereas ionization of (Z)-[(IPr)AuC(H)C(H)C(OMe)(4-C6H4OMe)2]+ formed 1-aryl-5-methoxy indene via an intramolecular Friedel-Crafts pathway.

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Publication details

The article was received on 31 Mar 2019, accepted on 08 May 2019 and first published on 10 May 2019


Article type: Edge Article
DOI: 10.1039/C9SC01574D
Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
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    Ionization of Gold (gamma-Methoxy)vinyl Complexes Generates Reactive Gold Vinyl Carbene Complexes

    R. Widenhoefer and N. Kim, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C9SC01574D

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