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On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

Title On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?
Authors Tiexin Li, Essam M. Dief, Zlatica Kalužná, Melanie MacGregor, Cina Foroutan-Nejad, Nadim Darwish
Magazine Langmuir
Date 04/26/2022
DOI 10.1021/acs.langmuir.2c00100
Introduction The 'click' azide-alkyne reaction is a popular method in various fields due to its simplicity, selectivity, and high yield, with copper(I) catalysts typically facilitating the formation of 1,4-disubstituted 1,2,3-triazole regioisomers. However, ruthenium-based catalysts have been developed to produce the 1,5-disubstituted isomer selectively. While ruthenium catalysis has been explored in solution, its efficacy for surface-based reactions remains uncertain, as do the electrical properties of the resulting isomers. In this study, we explore ruthenium catalysts for surface azide-alkyne reactions, aiming to produce 1,5-disubstituted triazoles and comparing their electrochemical properties with the copper-catalysed 1,4-isomer. Our findings reveal that ruthenium(II) complexes do catalyse surface reactions, but at a slower rate than copper, due to the size of the catalyst. The electron transfer rate constant for ruthenium is 30% that of copper, and the lower conductivity of the 1,5-isomer is supported by nonequilibrium Green's function computations. These results indicate the potential of ruthenium catalysis for surface reactions and suggest an electrical approach for distinguishing click reaction isomers.
Quote Tiexin Li, Essam M. Dief and Zlatica Kalužná et al. On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?. Langmuir. 2022. Vol. 38(18):5532-5541. DOI: 10.1021/acs.langmuir.2c00100
Element Copper (Cu) , Ruthenium (Ru)
Materials Chemical Compounds
Industry Chemical & Pharmacy , Research & Laboratory
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