Articles producció científica> Química Analítica i Química Orgànica

High-Yield Synthesis of a Long-Sought, Labile Ru-NHC Complex and Its Application to the Concise Synthesis of Second-Generation Olefin Metathesis Catalysts

  • Datos identificativos

    Identificador: imarina:9149602
    Handle: https://hdl.handle.net/20.500.11797/imarina9149602
    Autores:
    Day, Craig S.Fogg, Deryn E.
    Resumen:
    The controlled reaction of [RuCl2(p-cymene)](2) with H(2)IMes generates the previously challenging precatalyst and Ru synthon RuCl2(p-cymene)(H(2)IMes) (Ru-2) in 96% isolated yield. Critical to success is inhibiting premature p-cymene displacement. This is achieved by carrying out the synthesis at ambient temperatures, protected from light, and at sufficient dilutions (25 mM in THF) to enable stoichiometric control and inhibit bimolecular decomposition. The ease with which p-cymene loss can be deliberately induced, however, is key to the utility of Ru-2 in both catalysis and catalyst synthesis. The transformation of Ru-2 into two second-generation olefin metathesis catalysts is described. RuCl2(H(2)IMes)(=CH(o-C6H4-(OPr)-Pr-i)) (HII) and RuCl2(H(2)IMes)(PPh3)(=CHPh) GII' (a desirable, faster-initiating analogue of GII) are accessible in ca. 80% yield over two steps from commercially available [RuCl2(p-cymene)](2). Synthesis from RuCl2(PPh3)(3), in comparison, requires three or four steps for HII or GII', respectively, and proceeds in lower yields.

  • Otros:

    Autor según el artículo: Day, Craig S.; Fogg, Deryn E.;
    Departamento: Química Analítica i Química Orgànica
    Autor/es de la URV: Day, Craig
    Palabras clave: Ruthenium complexes Ring-closing metathesis Polymerization N-heterocyclic carbenes Ligands synthesis Hydrogenation Decomposition Chemical-shifts Acrylate metathesis Acceptor properties
    Resumen: The controlled reaction of [RuCl2(p-cymene)](2) with H(2)IMes generates the previously challenging precatalyst and Ru synthon RuCl2(p-cymene)(H(2)IMes) (Ru-2) in 96% isolated yield. Critical to success is inhibiting premature p-cymene displacement. This is achieved by carrying out the synthesis at ambient temperatures, protected from light, and at sufficient dilutions (25 mM in THF) to enable stoichiometric control and inhibit bimolecular decomposition. The ease with which p-cymene loss can be deliberately induced, however, is key to the utility of Ru-2 in both catalysis and catalyst synthesis. The transformation of Ru-2 into two second-generation olefin metathesis catalysts is described. RuCl2(H(2)IMes)(=CH(o-C6H4-(OPr)-Pr-i)) (HII) and RuCl2(H(2)IMes)(PPh3)(=CHPh) GII' (a desirable, faster-initiating analogue of GII) are accessible in ca. 80% yield over two steps from commercially available [RuCl2(p-cymene)](2). Synthesis from RuCl2(PPh3)(3), in comparison, requires three or four steps for HII or GII', respectively, and proceeds in lower yields.
    Áreas temáticas: Química Physical and theoretical chemistry Organic chemistry Materiais Inorganic chemistry Engenharias ii Ciências biológicas ii Ciências agrárias i Chemistry, organic Chemistry, inorganic & nuclear Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: craig.day@estudiants.urv.cat
    Identificador del autor: 0000-0002-6931-0280
    Página final: 4555
    Fecha de alta del registro: 2024-09-07
    Volumen de revista: 37
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Organometallics. 37 (24): 4551-4555
    Referencia de l'ítem segons les normes APA: Day, Craig S.; Fogg, Deryn E.; (2018). High-Yield Synthesis of a Long-Sought, Labile Ru-NHC Complex and Its Application to the Concise Synthesis of Second-Generation Olefin Metathesis Catalysts. Organometallics, 37(24), 4551-4555. DOI: 10.1021/acs.organomet.8b00745
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2018
    Página inicial: 4551
    Tipo de publicación: Journal Publications

  • Palabras clave:

    Chemistry, Inorganic & Nuclear,Chemistry, Organic,Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry
    Ruthenium complexes
    Ring-closing metathesis
    Polymerization
    N-heterocyclic carbenes
    Ligands synthesis
    Hydrogenation
    Decomposition
    Chemical-shifts
    Acrylate metathesis
    Acceptor properties
    Química
    Physical and theoretical chemistry
    Organic chemistry
    Materiais
    Inorganic chemistry
    Engenharias ii
    Ciências biológicas ii
    Ciências agrárias i
    Chemistry, organic
    Chemistry, inorganic & nuclear
    Astronomia / física

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