Investigation of Huisgen's Noble metal catalyst click reaction mechanism for the synthesis of 1,4-disubstituted 1,2,3-triazoles

Khairbek AA, Al-Zaben MI, Puchta R, Badawi MAAH, Thomas R (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Molecular Catalysis Elsevier

Book Volume: 566

Article Number: 114412

DOI: 10.1016/j.mcat.2024.114412

Abstract

The current study delves into the mechanistic intricacies of azide-alkyne cycloaddition reactions (MAAC) catalyzed by transition metals (M = Cu, Ag, and Au) bound to N-heterocyclic carbene (NHC) ligands, utilizing Density Functional Theory (DFT) calculations at the MN12-L/Def2-SVP level of theory, with Def2-TZVP for metal atoms, to shed light on the 1,4-regioisomer formation. A detailed comparison between mono- and bi-nuclear catalytic pathways for these metal complexes is presented. Our findings underscore the nuanced role of the metal identity in dictating the reaction's course, with a notable preference for a stepwise mechanism across the board, except in the mononuclear pathway of Au and Ag, which follows a concerted mechanism. The activation energies, analyzed in toluene solvent, underscore the efficiency of the binuclear pathway for all metals, showcasing significantly lower activation barriers (18.76 kcal/mol for Au and Ag, and 8.47 kcal/mol for Cu) compared to the mononuclear route. This distinction highlights the potential for optimizing catalytic performance through careful selection of metal-NHC combinations, providing valuable insights for the design of efficient catalysts in click chemistry applications. The study not only reaffirms the superior efficacy of the binuclear pathway but also enriches our understanding of metal-catalyzed MAAC reactions, contributing to the advancement of catalysis science and offering avenues for the development of novel synthetic strategies in organic chemistry.

Authors with CRIS profile

Ralph Puchta Lehrstuhl für Anorganische und Metallorganische Chemie

Involved external institutions

Tishreen University / جامعة تشرين SY Syrian Arab Republic (SY) King Saud University (KSU) / جامعة الملك سعود‎‎ SA Saudi Arabia (SA) St. Berchmans College IN India (IN)

How to cite

APA:

Khairbek, A.A., Al-Zaben, M.I., Puchta, R., Badawi, M.A.A.H., & Thomas, R. (2024). Investigation of Huisgen's Noble metal catalyst click reaction mechanism for the synthesis of 1,4-disubstituted 1,2,3-triazoles. Molecular Catalysis, 566. https://doi.org/10.1016/j.mcat.2024.114412

MLA:

Khairbek, Ali A., et al. "Investigation of Huisgen's Noble metal catalyst click reaction mechanism for the synthesis of 1,4-disubstituted 1,2,3-triazoles." Molecular Catalysis 566 (2024).

BibTeX: Download