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Mechanistic Insight into the Light-Triggered CuAAC Reaction, does any Photocatalyst go?

Authors: Martínez Haya, Rebeca; Heredia, Adrián Alberto; Castro Godoy, Willber David; Schmidt, Luciana Carina; Marin, María Luisa; Argüello, Juan Elias;

Mechanistic Insight into the Light-Triggered CuAAC Reaction, does any Photocatalyst go?

Abstract

The attainment of transition-metal catalysis and photoredox catalysis has represented a great challenge over the last years. Herein, we have been able to merge both catalytic processes into what we have called "the light-triggered CuAAC reaction". Particularly, the CuAAC reaction reveals opposite outcomes depending on the nature of the photocatalyst (eosin Y disodium salt and riboflavin tetraacetate) and additives (DABCO, Et3N, and NaN3) employed. To get a better insight into the operating processes, steady-state, time-resolved emission, and laser flash photolysis experiments have been performed to determine reactivity and kinetic data. These results, in agreement with thermodynamic estimations based on reported data, support the proposed mechanisms. While for eosin Y (EY), Cu(II) was reduced by its triplet excited state; for riboflavin tetraacetate (RFTA), mainly triplet excited RFTA state photoreductions by electron donors as additives are mandatory, affording RFTA•- (from DABCO and NaN3) or RFTAH• (from Et3N). Subsequently, these species are responsible for the reduction of Cu(II). For both photocatalysts, photogenerated Cu(I) finally renders 1,2,3-triazole as the final product. The determined kinetic rate constants allowed postulating plausible mechanisms in both cases, bringing to light the importance of kinetic studies to achieve a strong understanding of photoredox processes.

Fil: Heredia, Adrián Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina

Fil: Schmidt, Luciana Carina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina

Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina

Fil: Castro Godoy, Willber David. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad de El Salvador; El Salvador

Fil: Martínez Haya, Rebeca. Consejo Superior de Investigaciones Científicas. Instituto de Tecnología Química; España

Fil: Marin, María Luisa. Consejo Superior de Investigaciones Científicas. Instituto de Tecnología Química; España

Country
Argentina
Keywords

https://purl.org/becyt/ford/1.4, Photo-redox, CuAAC, https://purl.org/becyt/ford/1, Catalysis, Spectroscopy

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
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