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

Publication ,  Journal Article
Kim, N; Widenhoefer, RA
Published in: Chemical science
June 2019

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].

Duke Scholars

Published In

Chemical science

DOI

EISSN

2041-6539

ISSN

2041-6520

Publication Date

June 2019

Volume

10

Issue

24

Start / End Page

6149 / 6156

Related Subject Headings

  • 34 Chemical sciences
  • 03 Chemical Sciences
 

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Kim, N., & Widenhoefer, R. A. (2019). Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes. Chemical Science, 10(24), 6149–6156. https://doi.org/10.1039/c9sc01574d
Kim, Nana, and Ross A. Widenhoefer. “Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.Chemical Science 10, no. 24 (June 2019): 6149–56. https://doi.org/10.1039/c9sc01574d.
Kim N, Widenhoefer RA. Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes. Chemical science. 2019 Jun;10(24):6149–56.
Kim, Nana, and Ross A. Widenhoefer. “Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.Chemical Science, vol. 10, no. 24, June 2019, pp. 6149–56. Epmc, doi:10.1039/c9sc01574d.
Kim N, Widenhoefer RA. Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes. Chemical science. 2019 Jun;10(24):6149–6156.
Journal cover image

Published In

Chemical science

DOI

EISSN

2041-6539

ISSN

2041-6520

Publication Date

June 2019

Volume

10

Issue

24

Start / End Page

6149 / 6156

Related Subject Headings

  • 34 Chemical sciences
  • 03 Chemical Sciences