Molybdenum(VI) complexes with ligands derived from 5-(2-pyridyl)-2H-tetrazole as catalysts for the epoxidation of olefins

Detalhes bibliográficos
Autor(a) principal: Nunes, Martinique S.
Data de Publicação: 2023
Outros Autores: Gomes, Ana C., Neves, Patrícia, Mendes, Ricardo F., Almeida Paz, Filipe A., Lopes, André D., Pillinger, Martyn, Gonçalves, Isabel S., Valente, Anabela A.
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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spelling 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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