Logotipo do repositório
 

Publicação:
New dmso-ruthenium catalysts bearing N-heterocyclic carbene ligands for the ring-opening metathesis of norbornene

dc.contributor.authorCruz, Thais R. [UNESP]
dc.contributor.authorSilva, Rodolpho A. N. [UNESP]
dc.contributor.authorMachado, Antonio E. H.
dc.contributor.authorLima-Neto, Benedito S.
dc.contributor.authorGoi, Beatriz E. [UNESP]
dc.contributor.authorP. Carvalho, Valdemiro [UNESP]
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionUniversidade Federal de Uberlândia (UFU)
dc.contributor.institutionUniversidade de São Paulo (USP)
dc.date.accessioned2019-10-06T15:40:10Z
dc.date.available2019-10-06T15:40:10Z
dc.date.issued2019-01-01
dc.description.abstractNovel dimethyl sulfoxide ruthenium(ii) complexes of N-heterocyclic carbenes [RuCl2(S-dmso)2(SIMes)] (1), [RuCl2(S-dmso)2(IMes)], (2) [RuCl2(S-dmso)2(SIDip)] (3), and [RuCl2(S-dmso)2(IDip)] (4) were successfully synthesized. The complexes 1-4 were characterized by elemental analysis, FTIR, UV-Vis, 1H and 13C NMR, and computational studies. The polynorbornene (polyNBE) syntheses via ROMP using the complexes 1-4 as pre-catalysts in the presence of ethyl diazoacetate (EDA) were evaluated under different [EDA]/[Ru] and [NBE]/[Ru] ratios, temperatures (25 and 50 °C) and times (5-60 min). Quantitative yields of polyNBEs using [NBE]/[EDA]/[Ru] = 5000/28/1 for 10 min at 25 °C were obtained. The order of magnitude of 105 g mol−1 for Mn and PDI values ranging from 1.2 to 3.5 were measured by SEC. An investigation combining experimental data and computational calculations was performed to elucidate the mechanism of ROMP of NBE mediated by the complexes 1-4 as pre-catalysts. The proposed mechanism suggests the occurrence of a dissociative reaction of the complexes 1-4, losing a dmso ligand as the first step, resulting in a 14-electron species, which reacts with EDA to form the metal-carbene, followed by discoordination of the second dmso molecule for coordination of NBE.en
dc.description.affiliationFaculdade de Ciências e Tecnologia UNESP Univ Estadual Paulista
dc.description.affiliationInstituto de Química Universidade Federal de Uberlândia, P.O. Box 593
dc.description.affiliationInstituto de Química de São Carlos Universidade de São Paulo, CP 780
dc.description.affiliationUnespFaculdade de Ciências e Tecnologia UNESP Univ Estadual Paulista
dc.format.extent6220-6227
dc.identifierhttp://dx.doi.org/10.1039/c9nj00810a
dc.identifier.citationNew Journal of Chemistry, v. 43, n. 16, p. 6220-6227, 2019.
dc.identifier.doi10.1039/c9nj00810a
dc.identifier.issn1369-9261
dc.identifier.issn1144-0546
dc.identifier.scopus2-s2.0-85064394201
dc.identifier.urihttp://hdl.handle.net/11449/187560
dc.language.isoeng
dc.relation.ispartofNew Journal of Chemistry
dc.rights.accessRightsAcesso restritopt
dc.sourceScopus
dc.titleNew dmso-ruthenium catalysts bearing N-heterocyclic carbene ligands for the ring-opening metathesis of norborneneen
dc.typeArtigopt
dspace.entity.typePublication
unesp.author.lattes2452347030723060[5]
unesp.author.orcid0000-0003-4369-7824[5]
unesp.campusUniversidade Estadual Paulista (UNESP), Faculdade de Ciências e Tecnologia, Presidente Prudentept

Arquivos