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

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dc.contributor.authorLi, Tiexin
dc.contributor.authorDief, Essam M.
dc.contributor.authorKalužná, Zlatica
dc.contributor.authorMacGregor, Melanie
dc.contributor.authorForoutan-Nejad, Cina
dc.contributor.authorDarwish, Nadim
dc.contributor.organizationSchool of Molecular and Life Sciences, Curtin University, Bentley, Western Australiaen
dc.contributor.organizationFlinders Institute for Nanoscale Science & Technology, Flinders University, Bedford Park, South Australiaen
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciencesen
dc.contributor.organizationInstitute of Organic Chemistry and Biochemistry, Czech Academy of Sciencesen
dc.contributor.organizationUniversity of Warsaw, Faculty of Physicsen
dc.date.accessioned2022-11-15T12:56:45Z
dc.date.available2022-11-15T12:56:45Z
dc.date.issued2022
dc.description.abstractOwing to its simplicity, selectivity, high yield, and the absence of byproducts, the “click” azide–alkyne reaction is widely used in many areas. The reaction is usually catalyzed by copper(I), which selectively produces the 1,4-disubstituted 1,2,3-triazole regioisomer. Ruthenium-based catalysts were later developed to selectively produce the opposite regioselectivity─the 1,5-disubstituted 1,2,3-triazole isomer. Ruthenium-based catalysis, however, remains only tested for click reactions in solution, and the suitability of ruthenium catalysts for surface-based click reactions remains unknown. Also unknown are the electrical properties of the 1,4- and 1,5-regioisomers, and to measure them, both isomers need to be assembled on the electrode surface. Here, we test whether ruthenium catalysts can be used to catalyze surface azide–alkyne reactions to produce 1,5-disubstituted 1,2,3-triazole, and compare their electrochemical properties, in terms of surface coverages and electron transfer kinetics, to those of the compound formed by copper catalysis, 1,4-disubstituted 1,2,3-triazole isomer. Results show that ruthenium(II) complexes catalyze the click reaction on surfaces yielding the 1,5-disubstituted isomer, but the rate of the reaction is remarkably slower than that of the copper-catalyzed reaction, and this is related to the size of the catalyst involved as an intermediate in the reaction. The electron transfer rate constant (ket) for the ruthenium-catalyzed reaction is 30% of that measured for the copper-catalyzed 1,4-isomer. The lower conductivity of the 1,5-isomer is confirmed by performing nonequilibrium Green’s function computations on relevant model systems. These findings demonstrate the feasibility of ruthenium-based catalysis of surface click reactions and point toward an electrical method for detecting the isomers of click reactions.en
dc.description.sponsorshipAustralian Research Council (DP190100735 and FT200100301) National Science Centre, Poland 2020/39/B/ST4/02022 Czech Science Foundation Grant 21-17806S
dc.identifier.citationLangmuir 2022, 38, 18, 5532-5541 ; https://doi.org/10.1021/acs.langmuir.2c00100en
dc.identifier.doi10.1021/acs.langmuir.2c00100
dc.identifier.issn1520-5827
dc.identifier.issn0743-7463
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/21868
dc.language.isoen
dc.publisherAmerican Chemical Societyen
dc.rightsUznanie autorstwa 4.0 Międzynarodowe*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.titleOn-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?en
dc.typearticleen
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