A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation
Autor(a) principal: | |
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Data de Publicação: | 2018 |
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/10773/26353 |
Resumo: | The molybdenum(0)-carbonyl-triazole complexes [Mo(CO)₃(L)₃] [L = 1,2,3-triazole (1,2,3-trz) or 1,2,4-triazole (1,2,4-trz)] have been prepared and examined as precursors to molybdenum(VI) oxide catalysts for the epoxidation of cis-cyclooctene. Reaction of the carbonyl complexes with the oxidant tert-butyl hydroperoxide (TBHP) (either separately or in situ) gives oxomolybdenum(VI) hybrid materials that are proposed to possess one-dimensional polymeric structures in which adjacent oxo-bridged dioxomolybdenum(VI) moieties are further linked by bidentate bridging triazole (trz) ligands. A pronounced ligand influence on catalytic performance was found and the best result (quantitative epoxide yield within 1 h at 70 °C) was obtained with the 1,2,3-triazole oxomolybdenum(VI) hybrid. Both molybdenum oxide-triazole compounds displayed superior catalytic performance in comparison with the known hybrid materials [MoO₃(trz)0.5], which have different structures based on organic-inorganic perovskite-like layers. With aqueous H₂O₂ as the oxidant instead of TBHP, all compounds were completely soluble and active. A pronounced ligand influence on catalytic performance was only found for the hybrids [MoO₃(trz)0.5], and only the 1,2,4-trz compound displayed reaction-induced self-precipitation behavior. An insight into the type of solution species that may be involved in the catalytic processes with these compounds was obtained by separately treating [MoO₃(1,2,4-trz)0.5] with excess H₂O₂, which led to the crystallization of the complex (NH₄)1.8(H₃O)0.2[Mo₂O₂(μ₂-O)(O₂)₄(1,2,4-trz)]·H₂O. The single-crystal X-ray investigation of this complex reveals an oxo-bridged dinuclear structure with oxodiperoxo groups being further linked by a single triazole bridge. |
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A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidationMolybdenumTriazoleCarbonyl complexesOxidative decarbonylationEpoxidationThe molybdenum(0)-carbonyl-triazole complexes [Mo(CO)₃(L)₃] [L = 1,2,3-triazole (1,2,3-trz) or 1,2,4-triazole (1,2,4-trz)] have been prepared and examined as precursors to molybdenum(VI) oxide catalysts for the epoxidation of cis-cyclooctene. Reaction of the carbonyl complexes with the oxidant tert-butyl hydroperoxide (TBHP) (either separately or in situ) gives oxomolybdenum(VI) hybrid materials that are proposed to possess one-dimensional polymeric structures in which adjacent oxo-bridged dioxomolybdenum(VI) moieties are further linked by bidentate bridging triazole (trz) ligands. A pronounced ligand influence on catalytic performance was found and the best result (quantitative epoxide yield within 1 h at 70 °C) was obtained with the 1,2,3-triazole oxomolybdenum(VI) hybrid. Both molybdenum oxide-triazole compounds displayed superior catalytic performance in comparison with the known hybrid materials [MoO₃(trz)0.5], which have different structures based on organic-inorganic perovskite-like layers. With aqueous H₂O₂ as the oxidant instead of TBHP, all compounds were completely soluble and active. A pronounced ligand influence on catalytic performance was only found for the hybrids [MoO₃(trz)0.5], and only the 1,2,4-trz compound displayed reaction-induced self-precipitation behavior. An insight into the type of solution species that may be involved in the catalytic processes with these compounds was obtained by separately treating [MoO₃(1,2,4-trz)0.5] with excess H₂O₂, which led to the crystallization of the complex (NH₄)1.8(H₃O)0.2[Mo₂O₂(μ₂-O)(O₂)₄(1,2,4-trz)]·H₂O. The single-crystal X-ray investigation of this complex reveals an oxo-bridged dinuclear structure with oxodiperoxo groups being further linked by a single triazole bridge.MDPI2019-08-01T12:08:51Z2018-12-28T00:00:00Z2018-12-28info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/26353eng1420-304910.3390/molecules24010105Nogueira, Lucie SNeves, PatríciaGomes, Ana C.Amarante, Tatiana APaz, Filipe A. AlmeidaValente, Anabela A.Gonçalves, Isabel S.Pillinger, Martyninfo: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:RCAAP2023-07-17T04:00:47ZPortal AgregadorONG |
dc.title.none.fl_str_mv |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
title |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
spellingShingle |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation Nogueira, Lucie S Molybdenum Triazole Carbonyl complexes Oxidative decarbonylation Epoxidation |
title_short |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
title_full |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
title_fullStr |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
title_full_unstemmed |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
title_sort |
A comparative study of molybdenum carbonyl and oxomolybdenum derivatives bearing 1,2,3-triazole or 1,2,4-triazole in catalytic olefin epoxidation |
author |
Nogueira, Lucie S |
author_facet |
Nogueira, Lucie S Neves, Patrícia Gomes, Ana C. Amarante, Tatiana A Paz, Filipe A. Almeida Valente, Anabela A. Gonçalves, Isabel S. Pillinger, Martyn |
author_role |
author |
author2 |
Neves, Patrícia Gomes, Ana C. Amarante, Tatiana A Paz, Filipe A. Almeida Valente, Anabela A. Gonçalves, Isabel S. Pillinger, Martyn |
author2_role |
author author author author author author author |
dc.contributor.author.fl_str_mv |
Nogueira, Lucie S Neves, Patrícia Gomes, Ana C. Amarante, Tatiana A Paz, Filipe A. Almeida Valente, Anabela A. Gonçalves, Isabel S. Pillinger, Martyn |
dc.subject.por.fl_str_mv |
Molybdenum Triazole Carbonyl complexes Oxidative decarbonylation Epoxidation |
topic |
Molybdenum Triazole Carbonyl complexes Oxidative decarbonylation Epoxidation |
description |
The molybdenum(0)-carbonyl-triazole complexes [Mo(CO)₃(L)₃] [L = 1,2,3-triazole (1,2,3-trz) or 1,2,4-triazole (1,2,4-trz)] have been prepared and examined as precursors to molybdenum(VI) oxide catalysts for the epoxidation of cis-cyclooctene. Reaction of the carbonyl complexes with the oxidant tert-butyl hydroperoxide (TBHP) (either separately or in situ) gives oxomolybdenum(VI) hybrid materials that are proposed to possess one-dimensional polymeric structures in which adjacent oxo-bridged dioxomolybdenum(VI) moieties are further linked by bidentate bridging triazole (trz) ligands. A pronounced ligand influence on catalytic performance was found and the best result (quantitative epoxide yield within 1 h at 70 °C) was obtained with the 1,2,3-triazole oxomolybdenum(VI) hybrid. Both molybdenum oxide-triazole compounds displayed superior catalytic performance in comparison with the known hybrid materials [MoO₃(trz)0.5], which have different structures based on organic-inorganic perovskite-like layers. With aqueous H₂O₂ as the oxidant instead of TBHP, all compounds were completely soluble and active. A pronounced ligand influence on catalytic performance was only found for the hybrids [MoO₃(trz)0.5], and only the 1,2,4-trz compound displayed reaction-induced self-precipitation behavior. An insight into the type of solution species that may be involved in the catalytic processes with these compounds was obtained by separately treating [MoO₃(1,2,4-trz)0.5] with excess H₂O₂, which led to the crystallization of the complex (NH₄)1.8(H₃O)0.2[Mo₂O₂(μ₂-O)(O₂)₄(1,2,4-trz)]·H₂O. The single-crystal X-ray investigation of this complex reveals an oxo-bridged dinuclear structure with oxodiperoxo groups being further linked by a single triazole bridge. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-12-28T00:00:00Z 2018-12-28 2019-08-01T12:08:51Z |
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/10773/26353 |
url |
http://hdl.handle.net/10773/26353 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1420-3049 10.3390/molecules24010105 |
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 |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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