Autor segons l'article: Martinez-Espinar, Francisco; Salom-Catala, Antoni; Breso-Femenia, Emma; Claver, Carmen; Baletto, Francesca; Ricart, Josep M; Chaudret, Bruno; Carbo, Jorge J; Godard, Cyril; Castillon, Sergio
Departament: Química Analítica i Química Orgànica Química Física i Inorgànica
Autor/s de la URV: Alkhoury, Nadine / Carbó Martin, Jorge Juan / Castillón Miranda, Sergio / Claver Cabrero, Maria del Carmen Orosia / Godard, Cyril / Ricart Pla, Jose Manuel / Salom Català, Antoni
Paraules clau: H bond activation stabilized rh nanoparticles ruthenium nanoparticles phosphorus ligands phosphine iridium complexes hydrogenation electronic-structure c-h benzene
Resum: Ru and Rh nanoparticles catalyze the selective H/D exchange in phosphines using D2 as the deuterium source. The position of the deuterium incorporation is determined by the structure of the P-based substrates, while activity depends on the nature of the metal, the properties of the stabilizing agents, and the type of the substituent on phosphorus. The appropriate catalyst can thus be selected either for the exclusive H/D exchange in aromatic rings or also for alkyl substituents. The selectivity observed in each case provides relevant information on the coordination mode of the ligand. Density functional theory calculations provide insights into the H/D exchange mechanism and reveal a strong influence of the phosphine structure on the selectivity. The isotope exchange proceeds via C-H bond activation at nanoparticle edges. Phosphines with strong coordination through the phosphorus atom such as PPh3 or PPh2Me show preferred deuteration at ortho positions of aromatic rings and at the methyl substituents. This selectivity is observed because the corresponding C-H moieties can interact with the nanoparticle surface while the phosphine is P-coordinated, and the C-H activation results in stable metallacyclic intermediates. For weakly coordinating phosphines such as P(o-tolyl)3, the interaction with the nanoparticle can occur directly through phosphine substituents, and then, other deuteration patterns are observed.
Àrees temàtiques: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: nadine.alkhoury@estudiants.urv.cat nadine.alkhoury@estudiants.urv.cat nadine.alkhoury@estudiants.urv.cat nadine.alkhoury@estudiants.urv.cat antoni.salom@estudiants.urv.cat antoni.salom@estudiants.urv.cat cyril.godard@urv.cat j.carbo@urv.cat josep.ricart@urv.cat sergio.castillon@urv.cat carmen.claver@urv.cat
Identificador de l'autor: 0000-0001-5762-4904 0000-0002-3945-6721 0000-0002-2610-5535 0000-0002-0690-7549 0000-0002-2518-7401
Data d'alta del registre: 2024-10-12
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04442
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Inorganic Chemistry. 62 (11): 4570-4580
Referència de l'ítem segons les normes APA: Martinez-Espinar, Francisco; Salom-Catala, Antoni; Breso-Femenia, Emma; Claver, Carmen; Baletto, Francesca; Ricart, Josep M; Chaudret, Bruno; Carbo, J (2023). Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell. Inorganic Chemistry, 62(11), 4570-4580. DOI: 10.1021/acs.inorgchem.2c04442
DOI de l'article: 10.1021/acs.inorgchem.2c04442
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2023
Tipus de publicació: Journal Publications