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

  • Identification data

    Identifier: imarina:9149602
    Authors:
    Day, Craig S.Fogg, Deryn E.
    Abstract:
    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.
  • Others:

    Author, as appears in the article.: Day, Craig S.; Fogg, Deryn E.;
    Department: Química Analítica i Química Orgànica
    URV's Author/s: Day, Craig
    Keywords: Ruthenium complexes Ring-closing metathesis Polymerization N-heterocyclic carbenes Ligands synthesis Hydrogenation Decomposition Chemical-shifts Acrylate metathesis Acceptor properties
    Abstract: 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.
    Thematic Areas: 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
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: craig.day@estudiants.urv.cat
    Author identifier: 0000-0002-6931-0280
    Last page: 4555
    Record's date: 2024-09-07
    Journal volume: 37
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.organomet.8b00745
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Organometallics. 37 (24): 4551-4555
    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
    Article's DOI: 10.1021/acs.organomet.8b00745
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2018
    First page: 4551
    Publication Type: Journal Publications
  • Keywords:

    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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