On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?
Owing 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 catal...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
| Language: | English |
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AMER CHEMICAL SOC
2022
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| Subjects: | |
| Online Access: | http://purl.org/au-research/grants/arc/DP190100735 http://hdl.handle.net/20.500.11937/90973 |
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| author | Li, Tiexin Dief, Essam M. Kalužná, Z. Macgregor, M. Foroutan-Nejad, C. Darwish, Nadim |
| author_facet | Li, Tiexin Dief, Essam M. Kalužná, Z. Macgregor, M. Foroutan-Nejad, C. Darwish, Nadim |
| author_sort | Li, Tiexin |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Owing 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. |
| first_indexed | 2025-11-14T11:35:51Z |
| format | Journal Article |
| id | curtin-20.500.11937-90973 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T11:35:51Z |
| publishDate | 2022 |
| publisher | AMER CHEMICAL SOC |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-909732023-05-11T03:25:43Z On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts? Li, Tiexin Dief, Essam M. Kalužná, Z. Macgregor, M. Foroutan-Nejad, C. Darwish, Nadim Science & Technology Physical Sciences Technology Chemistry, Multidisciplinary Chemistry, Physical Materials Science, Multidisciplinary Chemistry Materials Science ELECTROSTATIC CATALYSIS MOLECULAR RULERS SILICON SURFACES SINGLE-MOLECULE BASIS-SETS MONOLAYERS CHEMISTRY ELECTRODES FUNCTIONALIZATION MECHANISM Owing 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. 2022 Journal Article http://hdl.handle.net/20.500.11937/90973 10.1021/acs.langmuir.2c00100 English http://purl.org/au-research/grants/arc/DP190100735 http://creativecommons.org/licenses/by/4.0/ AMER CHEMICAL SOC fulltext |
| spellingShingle | Science & Technology Physical Sciences Technology Chemistry, Multidisciplinary Chemistry, Physical Materials Science, Multidisciplinary Chemistry Materials Science ELECTROSTATIC CATALYSIS MOLECULAR RULERS SILICON SURFACES SINGLE-MOLECULE BASIS-SETS MONOLAYERS CHEMISTRY ELECTRODES FUNCTIONALIZATION MECHANISM Li, Tiexin Dief, Essam M. Kalužná, Z. Macgregor, M. Foroutan-Nejad, C. Darwish, Nadim 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? |
| title_full | On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts? |
| title_fullStr | On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts? |
| title_full_unstemmed | On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts? |
| title_short | On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts? |
| title_sort | on-surface azide-alkyne cycloaddition reaction: does it click with ruthenium catalysts? |
| topic | Science & Technology Physical Sciences Technology Chemistry, Multidisciplinary Chemistry, Physical Materials Science, Multidisciplinary Chemistry Materials Science ELECTROSTATIC CATALYSIS MOLECULAR RULERS SILICON SURFACES SINGLE-MOLECULE BASIS-SETS MONOLAYERS CHEMISTRY ELECTRODES FUNCTIONALIZATION MECHANISM |
| url | http://purl.org/au-research/grants/arc/DP190100735 http://hdl.handle.net/20.500.11937/90973 |