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: Acceptor properties Acrylate metathesis Chemical-shifts Decomposition Hydrogenation Ligands synthesis N-heterocyclic carbenes Polymerization Ring-closing metathesis Ruthenium complexes

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: Astronomia / física Chemistry, inorganic & nuclear Chemistry, organic Ciências agrárias i Ciências biológicas ii Engenharias ii Inorganic chemistry Materiais Organic chemistry Physical and theoretical chemistry Química

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

Record's date: 2021-10-10

Last page: 4555

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

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

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Article's DOI: 10.1021/acs.organomet.8b00745

Entity: Universitat Rovira i Virgili

Journal publication year: 2018

First page: 4551

Publication Type: Journal Publications