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Title: Au-iClick mirrors the mechanism of copper catalyzed azide–alkyne cycloaddition (CuAAC)

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/c5dt02405f· OSTI ID:1225600
 [1];  [1];  [1];  [1]
  1. Univ. of Florida, Gainesville, FL (United States)
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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.

Research Organization:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0010510
OSTI ID:
1225600
Journal Information:
Dalton Transactions, Vol. 44, Issue 33; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 34 works
Citation information provided by
Web of Science

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Cited By (6)

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 journal April 2017
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 journal January 2020
Photophysical and photochemical studies of tricarbonyl rhenium( i ) N-heterocyclic carbene complexes containing azide and triazolate ligands journal January 2016
Catalyst-free room-temperature iClick reaction of molybdenum( ii ) and tungsten( ii ) azide complexes with electron-poor alkynes: structural preferences and kinetic studies journal January 2017
Arylhydrazone ligands as Cu-protectors and -catalysis promoters in the azide–alkyne cycloaddition reaction journal January 2019
IClick cycloaddition reaction of light-triggered manganese( i ) carbonyl complexes journal January 2018

Linked Research (1)

Figures / Tables (13)

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Scheme 1(p. 1)figure Scheme 1
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Scheme 2(p. 2)figure Scheme 2
Figure 4(p. 3)figure Figure 4
Figure 5(p. 3)figure Figure 5
Figure 6(p. 3)figure Figure 6
Figure 7(p. 3)figure Figure 7
Figure 8(p. 3)figure Figure 8
Scheme 3(p. 3)figure Scheme 3
Figure 10(p. 4)figure Figure 10
Figure 9(p. 4)figure Figure 9

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY