A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins

Detalhes bibliográficos
Autor(a) principal: Nunes, Martinique S.
Data de Publicação: 2021
Outros Autores: Gomes, Diana M., Gomes, Ana C., Neves, Patrícia, Mendes, Ricardo F., Paz, Filipe A. Almeida, Lopes, A. D., Valente, Anabela A., Gonçalves, Isabel S., Pillinger, Martyn
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10400.1/17381
Resumo: There is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H2pytz)[MoO2Cl2 (pytz)] (1) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO3 (Hpytz)] (2). In addition to single-crystal X-ray diffraction (for 1), compounds 1 and 2 were characterized by FT-IR and Raman spectroscopies, solid-state 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds 1 and 2 were evaluated as olefin epoxidation catalysts using the model reaction of cis-cyclooctene (Cy8) with tert-butyl hydroperoxide (TBHP), at 70 ◦C, which gave 100% epoxide selectivity up to 100% conversion. While 1 behaved as a homogeneous catalyst, hybrid 2 behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene DL-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.
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spelling A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of OlefinsUm complexo de tetrazolato 5-(2-Pyridyl) de Molbdenum(VI), sua estrutura e transformação para um catalisador heterogêneo híbrido baseado em óxido de Molbdenum para a Epóxidação de OlefinsMolybdenumMolybdenum oxideOrganic-inorganic hybrid materialTetrazole5-(2-pyridyl) tetrazoleHydrogen bondsEpoxidationBio-olefinsThere is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H2pytz)[MoO2Cl2 (pytz)] (1) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO3 (Hpytz)] (2). In addition to single-crystal X-ray diffraction (for 1), compounds 1 and 2 were characterized by FT-IR and Raman spectroscopies, solid-state 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds 1 and 2 were evaluated as olefin epoxidation catalysts using the model reaction of cis-cyclooctene (Cy8) with tert-butyl hydroperoxide (TBHP), at 70 ◦C, which gave 100% epoxide selectivity up to 100% conversion. While 1 behaved as a homogeneous catalyst, hybrid 2 behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene DL-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.MDPISapientiaNunes, Martinique S.Gomes, Diana M.Gomes, Ana C.Neves, PatríciaMendes, Ricardo F.Paz, Filipe A. AlmeidaLopes, A. D.Valente, Anabela A.Gonçalves, Isabel S.Pillinger, Martyn2021-12-13T14:38:11Z2021-112021-11-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.1/17381eng10.3390/catal111114072073-4344info: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:RCAAP2023-07-24T10:29:31Zoai:sapientia.ualg.pt:10400.1/17381Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:07:21.956248Repositório 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 A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
Um complexo de tetrazolato 5-(2-Pyridyl) de Molbdenum(VI), sua estrutura e transformação para um catalisador heterogêneo híbrido baseado em óxido de Molbdenum para a Epóxidação de Olefins
title A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
spellingShingle A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
Nunes, Martinique S.
Molybdenum
Molybdenum oxide
Organic-inorganic hybrid material
Tetrazole
5-(2-pyridyl) tetrazole
Hydrogen bonds
Epoxidation
Bio-olefins
title_short A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_full A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_fullStr A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_full_unstemmed A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
title_sort A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of Olefins
author Nunes, Martinique S.
author_facet Nunes, Martinique S.
Gomes, Diana M.
Gomes, Ana C.
Neves, Patrícia
Mendes, Ricardo F.
Paz, Filipe A. Almeida
Lopes, A. D.
Valente, Anabela A.
Gonçalves, Isabel S.
Pillinger, Martyn
author_role author
author2 Gomes, Diana M.
Gomes, Ana C.
Neves, Patrícia
Mendes, Ricardo F.
Paz, Filipe A. Almeida
Lopes, A. D.
Valente, Anabela A.
Gonçalves, Isabel S.
Pillinger, Martyn
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Sapientia
dc.contributor.author.fl_str_mv Nunes, Martinique S.
Gomes, Diana M.
Gomes, Ana C.
Neves, Patrícia
Mendes, Ricardo F.
Paz, Filipe A. Almeida
Lopes, A. D.
Valente, Anabela A.
Gonçalves, Isabel S.
Pillinger, Martyn
dc.subject.por.fl_str_mv Molybdenum
Molybdenum oxide
Organic-inorganic hybrid material
Tetrazole
5-(2-pyridyl) tetrazole
Hydrogen bonds
Epoxidation
Bio-olefins
topic Molybdenum
Molybdenum oxide
Organic-inorganic hybrid material
Tetrazole
5-(2-pyridyl) tetrazole
Hydrogen bonds
Epoxidation
Bio-olefins
description There is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H2pytz)[MoO2Cl2 (pytz)] (1) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO3 (Hpytz)] (2). In addition to single-crystal X-ray diffraction (for 1), compounds 1 and 2 were characterized by FT-IR and Raman spectroscopies, solid-state 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds 1 and 2 were evaluated as olefin epoxidation catalysts using the model reaction of cis-cyclooctene (Cy8) with tert-butyl hydroperoxide (TBHP), at 70 ◦C, which gave 100% epoxide selectivity up to 100% conversion. While 1 behaved as a homogeneous catalyst, hybrid 2 behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene DL-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.
publishDate 2021
dc.date.none.fl_str_mv 2021-12-13T14:38:11Z
2021-11
2021-11-01T00:00:00Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
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dc.identifier.uri.fl_str_mv http://hdl.handle.net/10400.1/17381
url http://hdl.handle.net/10400.1/17381
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.3390/catal11111407
2073-4344
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