Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Outros Autores: | , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1016/j.mcat.2018.01.032 http://hdl.handle.net/11449/170695 |
Resumo: | Dimethyl sulfoxide ruthenium(II) complexes of N-heterocyclic carbenes derived from cycloalkylamines (cycloalkyl = cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl (1d)) were synthesized: [RuCl2(S-dmso)2(IPent)] (2a), [RuCl2(S-dmso)2(IHex)] (2b), [RuCl2(S-dmso)2(IHept)] (2c), and [RuCl2(S-dmso)2(IOct)] (2d). The imidazolium salts 1a-1d were characterized by FTIR, UV–vis, and 1H and 13C NMR spectroscopy, while their respective dimethyl sulfoxide ruthenium(II) complexes (2a-2d) were characterized by elemental analysis, FTIR, UV–vis, 1H and 13C NMR, and cyclic voltammetry. The complexes 2a-2d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The polynorbornene (polyNBE) syntheses via ROMP using the complexes 2a-2d as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 μL), [NBE]/[Ru] = 5000 at 50 °C as a function of time. The polymerization of MMA via ATRP was conducted using the complexes 2a-2d in the presence of ethyl 2-bromoisobutyrate (EBiB) as the initiator. All tests were using the molar ratio [MMA]/[EBiB]/[Ru] = 1000/2/1 and conducted at 85 °C. The linear correlation of ln([MMA]0/[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-2d proceeds in a controlled manner. |
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Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligandsATRPMethyl methacrylateNorborneneROMPRuthenium complexesDimethyl sulfoxide ruthenium(II) complexes of N-heterocyclic carbenes derived from cycloalkylamines (cycloalkyl = cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl (1d)) were synthesized: [RuCl2(S-dmso)2(IPent)] (2a), [RuCl2(S-dmso)2(IHex)] (2b), [RuCl2(S-dmso)2(IHept)] (2c), and [RuCl2(S-dmso)2(IOct)] (2d). The imidazolium salts 1a-1d were characterized by FTIR, UV–vis, and 1H and 13C NMR spectroscopy, while their respective dimethyl sulfoxide ruthenium(II) complexes (2a-2d) were characterized by elemental analysis, FTIR, UV–vis, 1H and 13C NMR, and cyclic voltammetry. The complexes 2a-2d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The polynorbornene (polyNBE) syntheses via ROMP using the complexes 2a-2d as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 μL), [NBE]/[Ru] = 5000 at 50 °C as a function of time. The polymerization of MMA via ATRP was conducted using the complexes 2a-2d in the presence of ethyl 2-bromoisobutyrate (EBiB) as the initiator. All tests were using the molar ratio [MMA]/[EBiB]/[Ru] = 1000/2/1 and conducted at 85 °C. The linear correlation of ln([MMA]0/[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-2d proceeds in a controlled manner.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Faculdade de Ciências e Tecnologia UNESP Univ Estadual Paulista, CEP 19060-900Instituto de Química de São Carlos Universidade de São Paulo, CEP 13560-970Instituto de Química UFU Universidade Federal de Uberlândia, CEP 38400-902Faculdade de Ciências e Tecnologia UNESP Univ Estadual Paulista, CEP 19060-900Universidade Estadual Paulista (Unesp)Universidade de São Paulo (USP)Universidade Federal de Uberlândia (UFU)Idehara, André H.S. [UNESP]Gois, Patrik D.S. [UNESP]Fernandez, HenriqueGoi, Beatriz E. [UNESP]Machado, Antonio E.H.Lima-Neto, Benedito S.Carvalho, Valdemiro P. [UNESP]2018-12-11T16:52:01Z2018-12-11T16:52:01Z2018-04-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article135-143application/pdfhttp://dx.doi.org/10.1016/j.mcat.2018.01.032Molecular Catalysis, v. 448, p. 135-143.2468-8231http://hdl.handle.net/11449/17069510.1016/j.mcat.2018.01.0322-s2.0-850424188012-s2.0-85042418801.pdfScopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengMolecular Catalysis1,069info:eu-repo/semantics/openAccess2023-10-06T06:06:59Zoai:repositorio.unesp.br:11449/170695Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T14:10:04.997476Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
title |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
spellingShingle |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands Idehara, André H.S. [UNESP] ATRP Methyl methacrylate Norbornene ROMP Ruthenium complexes |
title_short |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
title_full |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
title_fullStr |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
title_full_unstemmed |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
title_sort |
Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands |
author |
Idehara, André H.S. [UNESP] |
author_facet |
Idehara, André H.S. [UNESP] Gois, Patrik D.S. [UNESP] Fernandez, Henrique Goi, Beatriz E. [UNESP] Machado, Antonio E.H. Lima-Neto, Benedito S. Carvalho, Valdemiro P. [UNESP] |
author_role |
author |
author2 |
Gois, Patrik D.S. [UNESP] Fernandez, Henrique Goi, Beatriz E. [UNESP] Machado, Antonio E.H. Lima-Neto, Benedito S. Carvalho, Valdemiro P. [UNESP] |
author2_role |
author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) Universidade de São Paulo (USP) Universidade Federal de Uberlândia (UFU) |
dc.contributor.author.fl_str_mv |
Idehara, André H.S. [UNESP] Gois, Patrik D.S. [UNESP] Fernandez, Henrique Goi, Beatriz E. [UNESP] Machado, Antonio E.H. Lima-Neto, Benedito S. Carvalho, Valdemiro P. [UNESP] |
dc.subject.por.fl_str_mv |
ATRP Methyl methacrylate Norbornene ROMP Ruthenium complexes |
topic |
ATRP Methyl methacrylate Norbornene ROMP Ruthenium complexes |
description |
Dimethyl sulfoxide ruthenium(II) complexes of N-heterocyclic carbenes derived from cycloalkylamines (cycloalkyl = cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl (1d)) were synthesized: [RuCl2(S-dmso)2(IPent)] (2a), [RuCl2(S-dmso)2(IHex)] (2b), [RuCl2(S-dmso)2(IHept)] (2c), and [RuCl2(S-dmso)2(IOct)] (2d). The imidazolium salts 1a-1d were characterized by FTIR, UV–vis, and 1H and 13C NMR spectroscopy, while their respective dimethyl sulfoxide ruthenium(II) complexes (2a-2d) were characterized by elemental analysis, FTIR, UV–vis, 1H and 13C NMR, and cyclic voltammetry. The complexes 2a-2d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The polynorbornene (polyNBE) syntheses via ROMP using the complexes 2a-2d as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 μL), [NBE]/[Ru] = 5000 at 50 °C as a function of time. The polymerization of MMA via ATRP was conducted using the complexes 2a-2d in the presence of ethyl 2-bromoisobutyrate (EBiB) as the initiator. All tests were using the molar ratio [MMA]/[EBiB]/[Ru] = 1000/2/1 and conducted at 85 °C. The linear correlation of ln([MMA]0/[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-2d proceeds in a controlled manner. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-12-11T16:52:01Z 2018-12-11T16:52:01Z 2018-04-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1016/j.mcat.2018.01.032 Molecular Catalysis, v. 448, p. 135-143. 2468-8231 http://hdl.handle.net/11449/170695 10.1016/j.mcat.2018.01.032 2-s2.0-85042418801 2-s2.0-85042418801.pdf |
url |
http://dx.doi.org/10.1016/j.mcat.2018.01.032 http://hdl.handle.net/11449/170695 |
identifier_str_mv |
Molecular Catalysis, v. 448, p. 135-143. 2468-8231 10.1016/j.mcat.2018.01.032 2-s2.0-85042418801 2-s2.0-85042418801.pdf |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Molecular Catalysis 1,069 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
135-143 application/pdf |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
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1808128326911393792 |