Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Outros Autores: | , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1002/aoc.6491 http://hdl.handle.net/11449/233749 |
Resumo: | The monometallic complex [Pd(L)(PPh3)] (mono-Pd) was synthesized using a potentially tridentate hydrazone (H2L) and used as precursor to prepare a heterobimetallic ruthenium (II)-palladium (II) complex [Cl2(p-cymene)Ru(μ-L)Pd (PPh3)] (Ru-Pd). Mono-Pd and Ru-Pd were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV–Vis), 1H, 13C{1H} and 31P{1H} nuclear magnetic ressonance(NMR) spectroscopy, elemental analysis, cyclic voltammetry, matrix-assisted laser desorption/ionization - time of flight (MALDI-TOF) mass spectrometry, and computational methods. The mono-Pd was additionally studied by single-crystal X-ray diffraction. The complex [RuCl2(p-cymene)(Isoniazid)] (mono-Ru) was also obtained following literature methods aiming a comparison in the catalytic activity. The ring opening metathesis polymerization (ROMP) of norbornene (NBE) using mono-Ru or Ru-Pd as precatalysts in the presence of ethyl diazoacetate (EDA) was evaluated as a function of time (10–60 min) using [NBE]/[EDA]/[Ru] = 5000/28/1 at 50°C. The time increases produced good yields of polyNBE, reaching 38% and 46% for mono-Ru and Ru-Pd, respectively. The polyNBE produced was measured by size-exclusion chromatography (SEC) and reached an order of magnitude of 105 g·mol−1 of Mn, with Ð values ranging from 2.51 to 1.86 for mono-Ru and from 3.50 to 1.66 for Ru-Pd. The catalytic activity of mono-Pd and Ru-Pd on ethylene polymerization was assessed with a range of [Al]/[Pd] molar ratio between 350 and 1750, 30–70°C temperature, 2 to 4 h reaction time, and total reaction volume of 25 and 50 ml. Mono-Pd achieved an activity of 22.80 kg PE (mol Pd)−1 h−1 at 60°C after 4 h using [Al]/[Pd] = 1050, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. For Ru-Pd, an activity of 20.35 kg PE (mol Pd)−1 h−1 at 60°C after 4 h was obtained using [Al]/[Pd] = 1750, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. Overall, Ru-Pd showed to be active in both ROMP and ethylene polymerization reactions, being categorized as a bifunctional catalyst. |
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Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerizationThe monometallic complex [Pd(L)(PPh3)] (mono-Pd) was synthesized using a potentially tridentate hydrazone (H2L) and used as precursor to prepare a heterobimetallic ruthenium (II)-palladium (II) complex [Cl2(p-cymene)Ru(μ-L)Pd (PPh3)] (Ru-Pd). Mono-Pd and Ru-Pd were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV–Vis), 1H, 13C{1H} and 31P{1H} nuclear magnetic ressonance(NMR) spectroscopy, elemental analysis, cyclic voltammetry, matrix-assisted laser desorption/ionization - time of flight (MALDI-TOF) mass spectrometry, and computational methods. The mono-Pd was additionally studied by single-crystal X-ray diffraction. The complex [RuCl2(p-cymene)(Isoniazid)] (mono-Ru) was also obtained following literature methods aiming a comparison in the catalytic activity. The ring opening metathesis polymerization (ROMP) of norbornene (NBE) using mono-Ru or Ru-Pd as precatalysts in the presence of ethyl diazoacetate (EDA) was evaluated as a function of time (10–60 min) using [NBE]/[EDA]/[Ru] = 5000/28/1 at 50°C. The time increases produced good yields of polyNBE, reaching 38% and 46% for mono-Ru and Ru-Pd, respectively. The polyNBE produced was measured by size-exclusion chromatography (SEC) and reached an order of magnitude of 105 g·mol−1 of Mn, with Ð values ranging from 2.51 to 1.86 for mono-Ru and from 3.50 to 1.66 for Ru-Pd. The catalytic activity of mono-Pd and Ru-Pd on ethylene polymerization was assessed with a range of [Al]/[Pd] molar ratio between 350 and 1750, 30–70°C temperature, 2 to 4 h reaction time, and total reaction volume of 25 and 50 ml. Mono-Pd achieved an activity of 22.80 kg PE (mol Pd)−1 h−1 at 60°C after 4 h using [Al]/[Pd] = 1050, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. For Ru-Pd, an activity of 20.35 kg PE (mol Pd)−1 h−1 at 60°C after 4 h was obtained using [Al]/[Pd] = 1750, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. Overall, Ru-Pd showed to be active in both ROMP and ethylene polymerization reactions, being categorized as a bifunctional catalyst.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Faculdade de Ciências e Tecnologia UNESP – Univ. Estadual PaulistaDepartamento de Química Universidade Federal do Triângulo MineiroInstituto de Química de São Carlos Universidade de São PauloInstituto de Química Universidade Federal de UberlândiaFaculdade de Ciências e Tecnologia UNESP – Univ. Estadual PaulistaFAPESP: 2018/06340-1FAPESP: 2018/19395-9Universidade Estadual Paulista (UNESP)Universidade Federal do Triângulo MineiroUniversidade de São Paulo (USP)Universidade Federal de Uberlândia (UFU)Gois, Patrik Dione de Santana [UNESP]Maia, Juliana Iris PereiraMasson, Gustavo Henrique Cicero [UNESP]Martins, Daniele MariaMachado, Antonio Eduardo da HoraGoi, Beatriz Eleutério [UNESP]Maia, Pedro Ivo da SilvaCarvalho-Jr, Valdemiro Pereira de [UNESP]2022-05-01T09:47:31Z2022-05-01T09:47:31Z2022-02-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1002/aoc.6491Applied Organometallic Chemistry, v. 36, n. 2, 2022.1099-07390268-2605http://hdl.handle.net/11449/23374910.1002/aoc.64912-s2.0-85118107874Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengApplied Organometallic Chemistryinfo:eu-repo/semantics/openAccess2024-06-19T12:44:41Zoai:repositorio.unesp.br:11449/233749Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T20:17:10.974536Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
title |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
spellingShingle |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization Gois, Patrik Dione de Santana [UNESP] |
title_short |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
title_full |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
title_fullStr |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
title_full_unstemmed |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
title_sort |
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization |
author |
Gois, Patrik Dione de Santana [UNESP] |
author_facet |
Gois, Patrik Dione de Santana [UNESP] Maia, Juliana Iris Pereira Masson, Gustavo Henrique Cicero [UNESP] Martins, Daniele Maria Machado, Antonio Eduardo da Hora Goi, Beatriz Eleutério [UNESP] Maia, Pedro Ivo da Silva Carvalho-Jr, Valdemiro Pereira de [UNESP] |
author_role |
author |
author2 |
Maia, Juliana Iris Pereira Masson, Gustavo Henrique Cicero [UNESP] Martins, Daniele Maria Machado, Antonio Eduardo da Hora Goi, Beatriz Eleutério [UNESP] Maia, Pedro Ivo da Silva Carvalho-Jr, Valdemiro Pereira de [UNESP] |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (UNESP) Universidade Federal do Triângulo Mineiro Universidade de São Paulo (USP) Universidade Federal de Uberlândia (UFU) |
dc.contributor.author.fl_str_mv |
Gois, Patrik Dione de Santana [UNESP] Maia, Juliana Iris Pereira Masson, Gustavo Henrique Cicero [UNESP] Martins, Daniele Maria Machado, Antonio Eduardo da Hora Goi, Beatriz Eleutério [UNESP] Maia, Pedro Ivo da Silva Carvalho-Jr, Valdemiro Pereira de [UNESP] |
description |
The monometallic complex [Pd(L)(PPh3)] (mono-Pd) was synthesized using a potentially tridentate hydrazone (H2L) and used as precursor to prepare a heterobimetallic ruthenium (II)-palladium (II) complex [Cl2(p-cymene)Ru(μ-L)Pd (PPh3)] (Ru-Pd). Mono-Pd and Ru-Pd were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV–Vis), 1H, 13C{1H} and 31P{1H} nuclear magnetic ressonance(NMR) spectroscopy, elemental analysis, cyclic voltammetry, matrix-assisted laser desorption/ionization - time of flight (MALDI-TOF) mass spectrometry, and computational methods. The mono-Pd was additionally studied by single-crystal X-ray diffraction. The complex [RuCl2(p-cymene)(Isoniazid)] (mono-Ru) was also obtained following literature methods aiming a comparison in the catalytic activity. The ring opening metathesis polymerization (ROMP) of norbornene (NBE) using mono-Ru or Ru-Pd as precatalysts in the presence of ethyl diazoacetate (EDA) was evaluated as a function of time (10–60 min) using [NBE]/[EDA]/[Ru] = 5000/28/1 at 50°C. The time increases produced good yields of polyNBE, reaching 38% and 46% for mono-Ru and Ru-Pd, respectively. The polyNBE produced was measured by size-exclusion chromatography (SEC) and reached an order of magnitude of 105 g·mol−1 of Mn, with Ð values ranging from 2.51 to 1.86 for mono-Ru and from 3.50 to 1.66 for Ru-Pd. The catalytic activity of mono-Pd and Ru-Pd on ethylene polymerization was assessed with a range of [Al]/[Pd] molar ratio between 350 and 1750, 30–70°C temperature, 2 to 4 h reaction time, and total reaction volume of 25 and 50 ml. Mono-Pd achieved an activity of 22.80 kg PE (mol Pd)−1 h−1 at 60°C after 4 h using [Al]/[Pd] = 1050, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. For Ru-Pd, an activity of 20.35 kg PE (mol Pd)−1 h−1 at 60°C after 4 h was obtained using [Al]/[Pd] = 1750, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. Overall, Ru-Pd showed to be active in both ROMP and ethylene polymerization reactions, being categorized as a bifunctional catalyst. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-05-01T09:47:31Z 2022-05-01T09:47:31Z 2022-02-01 |
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/10.1002/aoc.6491 Applied Organometallic Chemistry, v. 36, n. 2, 2022. 1099-0739 0268-2605 http://hdl.handle.net/11449/233749 10.1002/aoc.6491 2-s2.0-85118107874 |
url |
http://dx.doi.org/10.1002/aoc.6491 http://hdl.handle.net/11449/233749 |
identifier_str_mv |
Applied Organometallic Chemistry, v. 36, n. 2, 2022. 1099-0739 0268-2605 10.1002/aoc.6491 2-s2.0-85118107874 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Applied Organometallic Chemistry |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
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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1808129184368689152 |