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Cationic copper iminophosphorane complexes as CuAAC catalysts: A mechanistic study
DOI:
10.1021/acs.organomet.0c00348
Authors:
Bas
Venderbosch
(University of Amsterdam)
,
Jean-pierre H.
Oudsen
(University of Amsterdam)
,
Jarl Ivar
Van Der Vlugt
(University of Amsterdam)
,
Ties J.
Korstanje
(University of Amsterdam)
,
Moniek
Tromp
(University of Amsterdam)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Organometallics
State:
Published (Approved)
Published:
September 2020
Diamond Proposal Number(s):
22432

Abstract: We have combined Cu K-edge X-ray absorption spectroscopy with NMR spectroscopy (1H and 31P) to study the Cu-catalyzed azide–alkyne cycloaddition (CuAAC) reaction under operando conditions. A variety of novel, well-defined CuI iminophosphorane complexes were prepared. These ligands, based on the in situ Staudinger reduction when [Cu(PPh3)3Br] is employed, were found to be active catalysts in the CuAAC reaction. Here, we highlight recent advances in mechanistic understanding of the CuAAC reaction using spectroscopic and kinetic investigations under strict air-free and operando conditions. A mononuclear Cu triazolide intermediate is identified to be the resting state during catalysis; cyclization and protonation both have an effect on the rate of the reaction. A key finding of this study includes a novel group of highly modular CuI complexes that are active in the base-free CuAAC reaction.
Journal Keywords: Azides; Hydrocarbons; Copper; Ligands; Pharmaceuticals
Subject Areas:
Chemistry
Instruments:
B18-Core EXAFS
Documents:
acs.organomet.0c00348.pdf