skip to main content

DOE PAGESDOE PAGES

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

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:
 [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Florida, Gainesville, FL (United States)
Publication Date:
OSTI Identifier:
1225600
Grant/Contract Number:
SC0010510
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
Research Org:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY