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
Autor(a) principal: | |
---|---|
Data de Publicação: | 2021 |
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/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. |
id |
RCAP_c1dd8213145fbe9a1e30b5859b768f2f |
---|---|
oai_identifier_str |
oai:sapientia.ualg.pt:10400.1/17381 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
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 |
status_str |
publishedVersion |
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 |
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 |
MDPI |
publisher.none.fl_str_mv |
MDPI |
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 |
|
_version_ |
1799133317755305984 |