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Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

  • Datos identificativos

    Identificador: imarina:9294241
    Autores:
    Martinez-Espinar, FranciscoSalom-Catala, AntoniBreso-Femenia, EmmaClaver, CarmenBaletto, FrancescaRicart, Josep MChaudret, BrunoCarbo, Jorge JGodard, CyrilCastillon, Sergio
    Resumen:
    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.
  • Otros:

    Autor según el artículo: 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
    Departamento: Química Analítica i Química Orgànica Química Física i Inorgànica
    Autor/es 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
    Palabras clave: H bond activation stabilized rh nanoparticles ruthenium nanoparticles phosphorus ligands phosphine iridium complexes hydrogenation electronic-structure c-h benzene
    Resumen: 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.
    Áreas temáticas: 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
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del 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 del autor: 0000-0001-5762-4904 0000-0002-3945-6721 0000-0002-2610-5535 0000-0002-0690-7549 0000-0002-2518-7401
    Fecha de alta del registro: 2024-10-12
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04442
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Inorganic Chemistry. 62 (11): 4570-4580
    Referencia 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 del artículo: 10.1021/acs.inorgchem.2c04442
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2023
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    H bond activation
    stabilized rh nanoparticles
    ruthenium nanoparticles
    phosphorus ligands
    phosphine
    iridium complexes
    hydrogenation
    electronic-structure
    c-h
    benzene
    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
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