Skip to Main content Skip to Navigation
Journal articles

Reaction Mechanisms of Transition-Metal-Catalyzed Azide-Alkyne Cycloaddition “Click” Reactions: A DFT Investigation

Abstract : DFT calculations at the PBE0/LANL2DZ level have been performed on model compounds to investigate the reaction mechanism of two recently reported metal-catalyzed alkyne azide cycloaddition (MAAC). The first one, that involves a [Cu(tren)]+Br- catalyst, is shown not to proceed through a metal alkynyl intermediate, but, after precomplexation of the alkyne in an η2-mode, directly to the 1,4-disubstituted 1,2,3-triazole product, through a metallacyclic transition state. The other system, involving a rare-earth Ln[N(SiMe3)2]3 complex, is found to proceed through an alkynyl-azide complex which produces an η 2-coordinated heterocyclic ligand before protonation by an incoming alkyne molecule. Our results are discussed with respect to other computational data from the literature
Document type :
Journal articles
Complete list of metadatas

Cited literature [46 references]  Display  Hide  Download

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01208404
Contributor : Laurent Jonchère <>
Submitted on : Thursday, December 3, 2015 - 2:30:18 PM
Last modification on : Friday, July 10, 2020 - 4:01:02 PM
Long-term archiving on: : Saturday, April 29, 2017 - 5:37:22 AM

File

Reaction Mechanisms of Transit...
Files produced by the author(s)

Identifiers

Citation

Djamila Ikhlef, Changlong Wang, Samia Kahlal, Boubekeur Maouche, Didier Astruc, et al.. Reaction Mechanisms of Transition-Metal-Catalyzed Azide-Alkyne Cycloaddition “Click” Reactions: A DFT Investigation. Computational and Theoretical Chemistry, Elsevier, 2015, 1073, pp.131-138. ⟨10.1016/j.comptc.2015.09.020⟩. ⟨hal-01208404⟩

Share

Metrics

Record views

343

Files downloads

426