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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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Supplementary files

Article information


Submitted
31 Mar 2019
Accepted
08 May 2019
First published
10 May 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 6149-6156
Article type
Edge Article

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

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