Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Outros Autores: | , , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10773/40437 |
Resumo: | The development of effective catalytic epoxidation processes that are an alternative to stoichiometric non-selective oxidation routes is important to meet environmental sustainability goals. In this work, molybdenum(VI) compounds bearing 5-(2-pyridyl)−2H-tetrazole derivatives as organic components, namely the ionic and neutral mononuclear complexes (H2ptz)[MoO2Cl2(ptz)] (1) and [MoO2Cl2(tBu-ptz)] (2), and the new Lindqvist-type polyoxometalate (POM) [tBu-Hptz]2[Mo6O19] (3), where Hptz = 5-(2-pyridyl)tetrazole and tBu-ptz = 2-tert-butyl-5-(2-pyridyl)−2H-tetrazole, were studied as epoxidation catalysts using readily available and relatively ecofriendly hydroperoxide oxidants, namely hydrogen peroxide and tert-butyl hydroperoxide (TBHP). The prepared catalysts were very active. For example, 100% cis-cyclooctene conversion and 100% epoxide selectivity were reached at 1 h for 1 and 3, and 10 min for 2 (with TBHP). Catalytic and characterization studies indicated that the mononuclear complexes suffered chemical transformations under the reaction conditions, whereas 3 was structurally stable. This POM acted as a homogeneous catalyst and could be recycled by employing an ionic liquid solvent. The POM can be synthesized from 2 under different conditions, including those used in the catalytic process. Moreover, 3 was an effective epoxidation catalyst for a biobased substrate scope that included fatty acid methyl esters and the terpene dl-limonene. |
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Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefinsBio-olefinsEpoxidationIonic liquidsLindqvist anionMolybdenumPyridyl-tetrazole ligandsThe development of effective catalytic epoxidation processes that are an alternative to stoichiometric non-selective oxidation routes is important to meet environmental sustainability goals. In this work, molybdenum(VI) compounds bearing 5-(2-pyridyl)−2H-tetrazole derivatives as organic components, namely the ionic and neutral mononuclear complexes (H2ptz)[MoO2Cl2(ptz)] (1) and [MoO2Cl2(tBu-ptz)] (2), and the new Lindqvist-type polyoxometalate (POM) [tBu-Hptz]2[Mo6O19] (3), where Hptz = 5-(2-pyridyl)tetrazole and tBu-ptz = 2-tert-butyl-5-(2-pyridyl)−2H-tetrazole, were studied as epoxidation catalysts using readily available and relatively ecofriendly hydroperoxide oxidants, namely hydrogen peroxide and tert-butyl hydroperoxide (TBHP). The prepared catalysts were very active. For example, 100% cis-cyclooctene conversion and 100% epoxide selectivity were reached at 1 h for 1 and 3, and 10 min for 2 (with TBHP). Catalytic and characterization studies indicated that the mononuclear complexes suffered chemical transformations under the reaction conditions, whereas 3 was structurally stable. This POM acted as a homogeneous catalyst and could be recycled by employing an ionic liquid solvent. The POM can be synthesized from 2 under different conditions, including those used in the catalytic process. Moreover, 3 was an effective epoxidation catalyst for a biobased substrate scope that included fatty acid methyl esters and the terpene dl-limonene.Elsevier2024-01-31T15:36:44Z2023-11-01T00:00:00Z2023-11-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/40437eng0920-586110.1016/j.cattod.2023.114273Nunes, Martinique S.Gomes, Ana C.Neves, PatríciaMendes, Ricardo F.Almeida Paz, Filipe A.Lopes, André D.Pillinger, MartynGonçalves, Isabel S.Valente, Anabela A.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-05-06T04:52:09Zoai:ria.ua.pt:10773/40437Portal AgregadorONGhttps://www.rcaap.pt/oai/openairemluisa.alvim@gmail.comopendoar:71602024-05-06T04:52:09Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
title |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
spellingShingle |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins Nunes, Martinique S. Bio-olefins Epoxidation Ionic liquids Lindqvist anion Molybdenum Pyridyl-tetrazole ligands |
title_short |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
title_full |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
title_fullStr |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
title_full_unstemmed |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
title_sort |
Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins |
author |
Nunes, Martinique S. |
author_facet |
Nunes, Martinique S. Gomes, Ana C. Neves, Patrícia Mendes, Ricardo F. Almeida Paz, Filipe A. Lopes, André D. Pillinger, Martyn Gonçalves, Isabel S. Valente, Anabela A. |
author_role |
author |
author2 |
Gomes, Ana C. Neves, Patrícia Mendes, Ricardo F. Almeida Paz, Filipe A. Lopes, André D. Pillinger, Martyn Gonçalves, Isabel S. Valente, Anabela A. |
author2_role |
author author author author author author author author |
dc.contributor.author.fl_str_mv |
Nunes, Martinique S. Gomes, Ana C. Neves, Patrícia Mendes, Ricardo F. Almeida Paz, Filipe A. Lopes, André D. Pillinger, Martyn Gonçalves, Isabel S. Valente, Anabela A. |
dc.subject.por.fl_str_mv |
Bio-olefins Epoxidation Ionic liquids Lindqvist anion Molybdenum Pyridyl-tetrazole ligands |
topic |
Bio-olefins Epoxidation Ionic liquids Lindqvist anion Molybdenum Pyridyl-tetrazole ligands |
description |
The development of effective catalytic epoxidation processes that are an alternative to stoichiometric non-selective oxidation routes is important to meet environmental sustainability goals. In this work, molybdenum(VI) compounds bearing 5-(2-pyridyl)−2H-tetrazole derivatives as organic components, namely the ionic and neutral mononuclear complexes (H2ptz)[MoO2Cl2(ptz)] (1) and [MoO2Cl2(tBu-ptz)] (2), and the new Lindqvist-type polyoxometalate (POM) [tBu-Hptz]2[Mo6O19] (3), where Hptz = 5-(2-pyridyl)tetrazole and tBu-ptz = 2-tert-butyl-5-(2-pyridyl)−2H-tetrazole, were studied as epoxidation catalysts using readily available and relatively ecofriendly hydroperoxide oxidants, namely hydrogen peroxide and tert-butyl hydroperoxide (TBHP). The prepared catalysts were very active. For example, 100% cis-cyclooctene conversion and 100% epoxide selectivity were reached at 1 h for 1 and 3, and 10 min for 2 (with TBHP). Catalytic and characterization studies indicated that the mononuclear complexes suffered chemical transformations under the reaction conditions, whereas 3 was structurally stable. This POM acted as a homogeneous catalyst and could be recycled by employing an ionic liquid solvent. The POM can be synthesized from 2 under different conditions, including those used in the catalytic process. Moreover, 3 was an effective epoxidation catalyst for a biobased substrate scope that included fatty acid methyl esters and the terpene dl-limonene. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-11-01T00:00:00Z 2023-11-01 2024-01-31T15:36:44Z |
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://hdl.handle.net/10773/40437 |
url |
http://hdl.handle.net/10773/40437 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
0920-5861 10.1016/j.cattod.2023.114273 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
mluisa.alvim@gmail.com |
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1817543889355014144 |