Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)
Abstract
This report outlines the investigation of the iClick mechanism between gold(I)-azides and gold(I)-acetylides to yield digold triazolates. Isolation of digold triazolate complexes offer compelling support for the role of two copper(I) ions in CuAAC. In addition, a kinetic investigation reveals the reaction is first order in both Au(I)-N3 and Au(I)-C≡C-R equivalent to C-R, thus second order overall. A Hammett plot with a ρ = 1.02(5) signifies electron-withdrawing groups accelerate the cycloaddition by facilitating the coordination of the second gold ion in a π-complex. Rate inhibition by the addition of free triphenylphosphine to the reaction indicates that ligand dissociation is a prerequisite for the reaction. The mechanistic conclusions mirror those proposed for the CuAAC reaction.
- Authors:
-
- Univ. of Florida, Gainesville, FL (United States)
- Publication Date:
- Research Org.:
- Univ. of Florida, Gainesville, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1225600
- Grant/Contract Number:
- SC0010510
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 44; Journal Issue: 33; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., and Veige, Adam S. Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC). United States: N. p., 2015.
Web. doi:10.1039/c5dt02405f.
Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., & Veige, Adam S. Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC). United States. https://doi.org/10.1039/c5dt02405f
Powers, Andrew R., Ghiviriga, Ion, Abboud, Khalil A., and Veige, Adam S. Mon .
"Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)". United States. https://doi.org/10.1039/c5dt02405f. https://www.osti.gov/servlets/purl/1225600.
@article{osti_1225600,
title = {Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)},
author = {Powers, Andrew R. and Ghiviriga, Ion and Abboud, Khalil A. and Veige, Adam S.},
abstractNote = {This report outlines the investigation of the iClick mechanism between gold(I)-azides and gold(I)-acetylides to yield digold triazolates. Isolation of digold triazolate complexes offer compelling support for the role of two copper(I) ions in CuAAC. In addition, a kinetic investigation reveals the reaction is first order in both Au(I)-N3 and Au(I)-C≡C-R equivalent to C-R, thus second order overall. A Hammett plot with a ρ = 1.02(5) signifies electron-withdrawing groups accelerate the cycloaddition by facilitating the coordination of the second gold ion in a π-complex. Rate inhibition by the addition of free triphenylphosphine to the reaction indicates that ligand dissociation is a prerequisite for the reaction. The mechanistic conclusions mirror those proposed for the CuAAC reaction.},
doi = {10.1039/c5dt02405f},
journal = {Dalton Transactions},
number = 33,
volume = 44,
place = {United States},
year = {Mon Jul 20 00:00:00 EDT 2015},
month = {Mon Jul 20 00:00:00 EDT 2015}
}
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Figures / Tables:
Figure 1: Generic iClick (A) and copper-catalyzed azide-alkyne cycloaddition (CuAAC; B).
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Works referencing / citing this record:
Electronic Influences on the Stability and Kinetics of Cp* Rhodium(III) Azide Complexes in the iClick Reaction with Electron-Poor Alkynes: Electronic Influences on the Stability and Kinetics of Cp* Rhodium(III) Azide Complexes in the iClick Reaction with Electron-Poor Alkynes
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Role of Sulfonate Appendage in the Protein Binding Affinity of Half-Sandwich Ruthenium(II)(η 6 - p -Cym) Complexes: Role of Sulfonate Appendage in the Protein Binding Affinity of Half-Sandwich Ruthenium(II)(η 6 - p -Cym) Complexes
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Photophysical and photochemical studies of tricarbonyl rhenium( i ) N-heterocyclic carbene complexes containing azide and triazolate ligands
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