Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation
Autor(a) principal: | |
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Data de Publicação: | 2019 |
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/10400.21/10351 |
Resumo: | Reactions between N6O4 macrocyclic 1,4,19,22,25,40-hexaaza-10,13,31,34-tetraoxa-6,14,27,35(1,4)-tetrabenzenacyclopentacontane (L) and several copper salts (viz. trifuoromethane and toluene sulfonates, nitrate, perchlorate, benzoate, and acetate) led to the formation of dinuclear compounds [Cu-2(OSO2CF3)(2)(DMF)(2)L](SO3CF3)(2) (1), [Cu-2(p-OSO2C6H4Me)(2)L(DMF)(2)](SO3C6H4Me)(2) (2), [Cu-2(ONO2)(2)L(DMF)(2)](NO3)(2) (3), [Cu-2(OClO3)(2)(DMF)(2)L](ClO4)(2) (4), [Cu-2(OOCPh)(2)L(H2O)(2)](O2CPh)(2) (5), and [Cu-2(OOCMe)(4)L] (6), which were characterized by IR, elemental analysis and TG-DTA (thermogravimetric-differential thermal analysis), as well as by single-crystal X-ray diffraction, EPR (electron paramagnetic resonance) spectroscopy, and electrochemical techniques (cyclic voltammetry and controlled potential electrolysis). The molecular structures of compounds 1-6 reveal a considerable conformational flexibility of the ligand L, which allowed its readjustment for the formation of the metal compounds and confirmed the presence of dinuclear endo macrocyclic species. In every case, the L ligand coordinates to each copper cation via three nitrogen atoms, with the remaining coordination positions of the metal square pyramid environment being accomplished by neutral or anionic ligands. The macrocyclic cavities appear to be adequate for the enclosure of a neutral species as proved by compound 6 with 1,4-dioxane. The compounds, in combination with the TEMPO (2,2,6,6-tetramethyl-piperidinyloxyl) radical and in alkaline aqueous solution, act as efficient catalysts in the aerobic oxidation of different alcohols to the corresponding aldehydes (yields up to 99% and TON up 232) after 20 h at 70 degrees C. In addition, the microwave-assisted solvent-free peroxidative oxidation (by tert-butylhydroperoxide, TBHP) of 1-phenylethanol led to acetophenone yields up to 99% and TOF of 1.1 x 10(3) after 0.5 h, without any additive. |
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Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidationMacrocyclicCopper complexesCatalysisAlcohol oxidationReactions between N6O4 macrocyclic 1,4,19,22,25,40-hexaaza-10,13,31,34-tetraoxa-6,14,27,35(1,4)-tetrabenzenacyclopentacontane (L) and several copper salts (viz. trifuoromethane and toluene sulfonates, nitrate, perchlorate, benzoate, and acetate) led to the formation of dinuclear compounds [Cu-2(OSO2CF3)(2)(DMF)(2)L](SO3CF3)(2) (1), [Cu-2(p-OSO2C6H4Me)(2)L(DMF)(2)](SO3C6H4Me)(2) (2), [Cu-2(ONO2)(2)L(DMF)(2)](NO3)(2) (3), [Cu-2(OClO3)(2)(DMF)(2)L](ClO4)(2) (4), [Cu-2(OOCPh)(2)L(H2O)(2)](O2CPh)(2) (5), and [Cu-2(OOCMe)(4)L] (6), which were characterized by IR, elemental analysis and TG-DTA (thermogravimetric-differential thermal analysis), as well as by single-crystal X-ray diffraction, EPR (electron paramagnetic resonance) spectroscopy, and electrochemical techniques (cyclic voltammetry and controlled potential electrolysis). The molecular structures of compounds 1-6 reveal a considerable conformational flexibility of the ligand L, which allowed its readjustment for the formation of the metal compounds and confirmed the presence of dinuclear endo macrocyclic species. In every case, the L ligand coordinates to each copper cation via three nitrogen atoms, with the remaining coordination positions of the metal square pyramid environment being accomplished by neutral or anionic ligands. The macrocyclic cavities appear to be adequate for the enclosure of a neutral species as proved by compound 6 with 1,4-dioxane. The compounds, in combination with the TEMPO (2,2,6,6-tetramethyl-piperidinyloxyl) radical and in alkaline aqueous solution, act as efficient catalysts in the aerobic oxidation of different alcohols to the corresponding aldehydes (yields up to 99% and TON up 232) after 20 h at 70 degrees C. In addition, the microwave-assisted solvent-free peroxidative oxidation (by tert-butylhydroperoxide, TBHP) of 1-phenylethanol led to acetophenone yields up to 99% and TOF of 1.1 x 10(3) after 0.5 h, without any additive.MDPIRCIPLMa, ZhenWang, QijunAlegria, ElisabeteGuedes Da Silva, M. Fátima C.Martins, LuisaJ. P. Telo, João P. Telo, João Paulo TeloCorreia, IsabelPombeiro, Armando2019-07-22T13:50:06Z2019-05-072019-05-07T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/10351engMA, Zhen; [et al] – Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation. Catalysts. ISSN 2073-4344. Vol. 9, N.º 5 (2019), pp. 1-232073-434410.3390/catal9050424metadata only accessinfo: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:RCAAP2023-08-03T10:00:11Zoai:repositorio.ipl.pt:10400.21/10351Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:18:47.550317Repositório 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 |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
title |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
spellingShingle |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation Ma, Zhen Macrocyclic Copper complexes Catalysis Alcohol oxidation |
title_short |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
title_full |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
title_fullStr |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
title_full_unstemmed |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
title_sort |
Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation |
author |
Ma, Zhen |
author_facet |
Ma, Zhen Wang, Qijun Alegria, Elisabete Guedes Da Silva, M. Fátima C. Martins, Luisa J. P. Telo, João P. Telo, João Paulo Telo Correia, Isabel Pombeiro, Armando |
author_role |
author |
author2 |
Wang, Qijun Alegria, Elisabete Guedes Da Silva, M. Fátima C. Martins, Luisa J. P. Telo, João P. Telo, João Paulo Telo Correia, Isabel Pombeiro, Armando |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Ma, Zhen Wang, Qijun Alegria, Elisabete Guedes Da Silva, M. Fátima C. Martins, Luisa J. P. Telo, João P. Telo, João Paulo Telo Correia, Isabel Pombeiro, Armando |
dc.subject.por.fl_str_mv |
Macrocyclic Copper complexes Catalysis Alcohol oxidation |
topic |
Macrocyclic Copper complexes Catalysis Alcohol oxidation |
description |
Reactions between N6O4 macrocyclic 1,4,19,22,25,40-hexaaza-10,13,31,34-tetraoxa-6,14,27,35(1,4)-tetrabenzenacyclopentacontane (L) and several copper salts (viz. trifuoromethane and toluene sulfonates, nitrate, perchlorate, benzoate, and acetate) led to the formation of dinuclear compounds [Cu-2(OSO2CF3)(2)(DMF)(2)L](SO3CF3)(2) (1), [Cu-2(p-OSO2C6H4Me)(2)L(DMF)(2)](SO3C6H4Me)(2) (2), [Cu-2(ONO2)(2)L(DMF)(2)](NO3)(2) (3), [Cu-2(OClO3)(2)(DMF)(2)L](ClO4)(2) (4), [Cu-2(OOCPh)(2)L(H2O)(2)](O2CPh)(2) (5), and [Cu-2(OOCMe)(4)L] (6), which were characterized by IR, elemental analysis and TG-DTA (thermogravimetric-differential thermal analysis), as well as by single-crystal X-ray diffraction, EPR (electron paramagnetic resonance) spectroscopy, and electrochemical techniques (cyclic voltammetry and controlled potential electrolysis). The molecular structures of compounds 1-6 reveal a considerable conformational flexibility of the ligand L, which allowed its readjustment for the formation of the metal compounds and confirmed the presence of dinuclear endo macrocyclic species. In every case, the L ligand coordinates to each copper cation via three nitrogen atoms, with the remaining coordination positions of the metal square pyramid environment being accomplished by neutral or anionic ligands. The macrocyclic cavities appear to be adequate for the enclosure of a neutral species as proved by compound 6 with 1,4-dioxane. The compounds, in combination with the TEMPO (2,2,6,6-tetramethyl-piperidinyloxyl) radical and in alkaline aqueous solution, act as efficient catalysts in the aerobic oxidation of different alcohols to the corresponding aldehydes (yields up to 99% and TON up 232) after 20 h at 70 degrees C. In addition, the microwave-assisted solvent-free peroxidative oxidation (by tert-butylhydroperoxide, TBHP) of 1-phenylethanol led to acetophenone yields up to 99% and TOF of 1.1 x 10(3) after 0.5 h, without any additive. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-07-22T13:50:06Z 2019-05-07 2019-05-07T00:00:00Z |
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/10400.21/10351 |
url |
http://hdl.handle.net/10400.21/10351 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
MA, Zhen; [et al] – Synthesis and structure of copper complexes of a N6O4 macrocyclic ligand and catalytic application in alcohol oxidation. Catalysts. ISSN 2073-4344. Vol. 9, N.º 5 (2019), pp. 1-23 2073-4344 10.3390/catal9050424 |
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metadata only access info:eu-repo/semantics/openAccess |
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metadata only access |
eu_rights_str_mv |
openAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
MDPI |
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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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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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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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