MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies

[EN] Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented...

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Authors: Ramírez-Grau, Rubén, García-Aznar, Pablo|||0000-0003-0586-0037, Sastre Navarro, German Ignacio|||0000-0003-0496-6331, Goberna-Ferrón, Sara|||0000-0002-3306-3791, Primo Arnau, Ana Maria|||0000-0001-9205-2278, García Gómez, Hermenegildo|||0000-0002-9664-493X, Pavel, Octavian, Tirsoaga, Alina, Cojocaru, Bogdan, Popescu, Dana Georgeta, Parvulescu, Vasile I.
Format: article
Publication Date:2025
Country:España
Institution:Universitat Politècnica de València (UPV)
Repository:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Language:English
OAI Identifier:oai:riunet.upv.es:10251/220209
Online Access:https://riunet.upv.es/handle/10251/220209
Access Level:Open access
Keyword:Intermolecular hydroamination
Photocatalytic activity
Direct addition
TI3C2
Surface
Degradation
Titanium
Enhancement
Precatalyst
Derivatives
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oai_identifier_str oai:riunet.upv.es:10251/220209
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
title MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
spellingShingle MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
Ramírez-Grau, Rubén
Intermolecular hydroamination
Photocatalytic activity
Direct addition
TI3C2
Surface
Degradation
Titanium
Enhancement
Precatalyst
Derivatives
title_short MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
title_full MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
title_fullStr MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
title_full_unstemmed MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
title_sort MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover Frequencies
dc.creator.none.fl_str_mv Ramírez-Grau, Rubén
García-Aznar, Pablo|||0000-0003-0586-0037
Sastre Navarro, German Ignacio|||0000-0003-0496-6331
Goberna-Ferrón, Sara|||0000-0002-3306-3791
Primo Arnau, Ana Maria|||0000-0001-9205-2278
García Gómez, Hermenegildo|||0000-0002-9664-493X
Pavel, Octavian
Tirsoaga, Alina
Cojocaru, Bogdan
Popescu, Dana Georgeta
Parvulescu, Vasile I.
author Ramírez-Grau, Rubén
author_facet Ramírez-Grau, Rubén
García-Aznar, Pablo|||0000-0003-0586-0037
Sastre Navarro, German Ignacio|||0000-0003-0496-6331
Goberna-Ferrón, Sara|||0000-0002-3306-3791
Primo Arnau, Ana Maria|||0000-0001-9205-2278
García Gómez, Hermenegildo|||0000-0002-9664-493X
Pavel, Octavian
Tirsoaga, Alina
Cojocaru, Bogdan
Popescu, Dana Georgeta
Parvulescu, Vasile I.
author_role author
author2 García-Aznar, Pablo|||0000-0003-0586-0037
Sastre Navarro, German Ignacio|||0000-0003-0496-6331
Goberna-Ferrón, Sara|||0000-0002-3306-3791
Primo Arnau, Ana Maria|||0000-0001-9205-2278
García Gómez, Hermenegildo|||0000-0002-9664-493X
Pavel, Octavian
Tirsoaga, Alina
Cojocaru, Bogdan
Popescu, Dana Georgeta
Parvulescu, Vasile I.
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Instituto Universitario Mixto de Tecnología Química
Escuela Técnica Superior de Ingeniería Industrial
Generalitat Valenciana
Agencia Estatal de Investigación
Universitat Politècnica de València
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Intermolecular hydroamination
Photocatalytic activity
Direct addition
TI3C2
Surface
Degradation
Titanium
Enhancement
Precatalyst
Derivatives
topic Intermolecular hydroamination
Photocatalytic activity
Direct addition
TI3C2
Surface
Degradation
Titanium
Enhancement
Precatalyst
Derivatives
description [EN] Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-01-21
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/220209
url https://riunet.upv.es/handle/10251/220209
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Generalitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2021%2F038
Generalitat Valenciana https://doi.org/10.13039/501100003359 MFA%2F2022%2F023
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 CEX2021-001230-S
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 PDI2021-0126071-OB-CO21
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento (by)
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 10 2 h-1 Turnover FrequenciesRamírez-Grau, RubénGarcía-Aznar, Pablo|||0000-0003-0586-0037Sastre Navarro, German Ignacio|||0000-0003-0496-6331Goberna-Ferrón, Sara|||0000-0002-3306-3791Primo Arnau, Ana Maria|||0000-0001-9205-2278García Gómez, Hermenegildo|||0000-0002-9664-493XPavel, OctavianTirsoaga, AlinaCojocaru, BogdanPopescu, Dana GeorgetaParvulescu, Vasile I.Intermolecular hydroaminationPhotocatalytic activityDirect additionTI3C2SurfaceDegradationTitaniumEnhancementPrecatalystDerivatives[EN] Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.Financial support was provided by UEFISCD, Ministry of Innovation and Science (Severo Ochoa CEX2021-001230-S and PDI2021-0126071-OB-CO2, both funded by MCIN/AEI/10.13039/501100011033), Generalitat Valenciana (Prometeo 2021-38 and Advanced Materials Programme Graphica MFA/2022/023 with funding from the European Union NextGenerationEU PRTR-C17.I1) are gratefully acknowledged. This study forms part of the Advanced Materials programme and was supported by MCIN with funding from the European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana. We thank CTI-CSIC and ASIC-UPV for their computational facilities. R.R.-G. and P. G.-A. are recipients of postgraduate scholarships awarded by the Spanish Ministry of Science and Innovation.American Chemical SocietyDepartamento de QuímicaInstituto Universitario Mixto de Tecnología QuímicaEscuela Técnica Superior de Ingeniería IndustrialGeneralitat ValencianaAgencia Estatal de InvestigaciónUniversitat Politècnica de ValènciaRepositorio Institucional de la Universitat Politècnica de València Riunet20252025-01-21journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/220209reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengGeneralitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2021%2F038Generalitat Valenciana https://doi.org/10.13039/501100003359 MFA%2F2022%2F023Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 CEX2021-001230-SAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 PDI2021-0126071-OB-CO21open accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento (by)http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/2202092026-06-13T07:49:27Z
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