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
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
Entity: Universitat Rovira i Virgili
Journal publication year: 2018
First page: 4551
Publication Type: Journal Publications
Repositori URV