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

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00557363" target="_blank" >RIV/61388963:_____/22:00557363 - isvavai.cz</a>

Result on the web

<a href="https://doi.org/10.1021/acs.langmuir.2c00100" target="_blank" >https://doi.org/10.1021/acs.langmuir.2c00100</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.langmuir.2c00100" target="_blank" >10.1021/acs.langmuir.2c00100</a>

Result language

angličtina

Original language name

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

Original language description

Owing to its simplicity, selectivity, high yield, and the absence of byproducts, the „clic“kazide-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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA21-17806S" target="_blank" >GA21-17806S: Endohedral Fullerenes for Molecular Components: Memristors and Spinristors</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Langmuir

ISSN

0743-7463

e-ISSN

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Volume of the periodical

38

Issue of the periodical within the volume

18

Country of publishing house

US - UNITED STATES

Number of pages

10

Pages from-to

5532-5541

UT code for WoS article

000813258400001

EID of the result in the Scopus database

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