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Issue 24, 2019
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Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes

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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 = 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 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 and the significant distribution of positive charge into the γ-anisyl rings. 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 the corresponding vinylcyclopropane. In the absence of nucleophile (E)-5a decomposed predominantly via intermolecular carbene dimerization whereas formation of 1-aryl-5-methoxy indene upon ionization of (Z)-(IPr)AuC(H)C(H)C(OMe)(4-C6H4OMe)2 [(Z)-6b] implicated an intramolecular Friedel–Crafts or electrocyclic Nazarov pathway for the decomposition of the unobserved vinyl carbene complex (Z)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf [(Z)-5b].

Graphical abstract: Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes

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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., 2019,10, 6149-6156
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes

    N. Kim and R. A. Widenhoefer, Chem. Sci., 2019, 10, 6149
    DOI: 10.1039/C9SC01574D

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

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