MXenes as Heterogeneous Thermal Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes with 102 h–1 Turnover FrequenciesClick to copy article linkArticle link copied!
- Rubén Ramírez GrauRubén Ramírez GrauInstituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by Rubén Ramírez Grau
- Pablo Garcia-AznarPablo Garcia-AznarInstituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by Pablo Garcia-Aznar
- German SastreGerman SastreInstituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by German Sastre
- Sara Goberna-FerrónSara Goberna-FerrónInstituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by Sara Goberna-Ferrón
- Octavian PavelOctavian PavelDepartment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030016, RomaniaMore by Octavian Pavel
- Alina TirsoagaAlina TirsoagaDepartment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030016, RomaniaMore by Alina Tirsoaga
- Bogdan CojocaruBogdan CojocaruDepartment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030016, RomaniaMore by Bogdan Cojocaru
- Dana Georgeta PopescuDana Georgeta PopescuNational Institute of Materials Physics, 405A Atomistilor Street, Magurele 077125, Ilfov, RomaniaMore by Dana Georgeta Popescu
- Vasile I. Parvulescu*Vasile I. Parvulescu*Email: [email protected]Department of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030016, RomaniaMore by Vasile I. Parvulescu
- Ana Primo*Ana Primo*Email: [email protected]Instituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by Ana Primo
- Hermenegildo García*Hermenegildo García*Email: [email protected]Instituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, SpainMore by Hermenegildo García
Abstract
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.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 1 publications.
- Virendra Kumar Yadav, Suhas Ballal, Rupesh Gupta, Subhashree Ray, Shivraj Gangadhar Wanale, Rakesh Gaur, Gajendra Kumar Inwati. Structural, Surface, and Morphological Investigations of Plasmon-Induced MXenes for Multifunctional Applications. Plasmonics 2025, 6 https://doi.org/10.1007/s11468-025-02947-z
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.