C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions
Autor(a) principal: | |
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Data de Publicação: | 2020 |
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/10400.21/12275 |
Resumo: | The new Au(III) complex [AuCl2(Tpms)] (1) and the previously reported [AuCl2(Tpm)]Cl (2), bearing the potentially tridentate ligands tris(1-pyrazolyl)methanesulfonate (SO3C(C3H3N2)(3)(-), Tpms) or hydrotris(1-pyrazolyl) methane (HC(C3H3N2)(3), Tpm), respectively, were synthesized in water at room temperature and characterized using NMR and IR spectroscopy. The molecular structure of 1 was authenticated by single crystal X-ray diffraction analysis. The catalytic performance of the Au(III) complexes was tested, for the first time, in toluene and benzyl alcohol oxidation reactions. The oxidative esterification of benzaldehyde, by-product of toluene oxidation, was further explored. In order to optimize the catalytic systems, the influence of parameters such as temperature, reaction time, amount of pre-catalyst and the presence of additives was evaluated. In the peroxidative (by H2O2 or t-BuOOH) oxidation reactions, a maximum total yield (benzylic alcohol and benzaldehyde) of 8% for toluene oxidation with pre-catalyst 1 (6 h, 80 degrees C, H2O2 30% aq. sol.) and a maximum total yield (benzaldehyde and benzoic acid) of 43% for benzyl alcohol oxidation with pre-catalyst 2 (24 h, 80 degrees C, t-BuOOH 70% aq. sol.) with a selectivity of 72% for benzaldehyde, were obtained. The esterification of benzaldehyde yielded, in the presence of 1, a maximum of 27% and 48% of methyl benzoate, at room temperature and 80 degrees C, respectively, and with a selectivity of 78% for methyl benzoate. |
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C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactionsGold(III) complexC-scorpionateToluene oxidationOxidative esterificationValue-added productThe new Au(III) complex [AuCl2(Tpms)] (1) and the previously reported [AuCl2(Tpm)]Cl (2), bearing the potentially tridentate ligands tris(1-pyrazolyl)methanesulfonate (SO3C(C3H3N2)(3)(-), Tpms) or hydrotris(1-pyrazolyl) methane (HC(C3H3N2)(3), Tpm), respectively, were synthesized in water at room temperature and characterized using NMR and IR spectroscopy. The molecular structure of 1 was authenticated by single crystal X-ray diffraction analysis. The catalytic performance of the Au(III) complexes was tested, for the first time, in toluene and benzyl alcohol oxidation reactions. The oxidative esterification of benzaldehyde, by-product of toluene oxidation, was further explored. In order to optimize the catalytic systems, the influence of parameters such as temperature, reaction time, amount of pre-catalyst and the presence of additives was evaluated. In the peroxidative (by H2O2 or t-BuOOH) oxidation reactions, a maximum total yield (benzylic alcohol and benzaldehyde) of 8% for toluene oxidation with pre-catalyst 1 (6 h, 80 degrees C, H2O2 30% aq. sol.) and a maximum total yield (benzaldehyde and benzoic acid) of 43% for benzyl alcohol oxidation with pre-catalyst 2 (24 h, 80 degrees C, t-BuOOH 70% aq. sol.) with a selectivity of 72% for benzaldehyde, were obtained. The esterification of benzaldehyde yielded, in the presence of 1, a maximum of 27% and 48% of methyl benzoate, at room temperature and 80 degrees C, respectively, and with a selectivity of 78% for methyl benzoate.ElsevierRCIPLLapa, HugoGuedes Da Silva, M. Fátima C.Pombeiro, ArmandoAlegria, ElisabeteMartins, Luisa2020-10-06T16:51:00Z2020-11-012020-11-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/12275engLAPA, Hugo M.; [et al] – C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions. Inorganica Chimica Acta. ISSN 0020-1693. Vol. 512 (2020), pp. 1-110020-169310.1016/j.ica.2020.119881metadata 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:RCAAP2023-08-03T10:04:52Zoai:repositorio.ipl.pt:10400.21/12275Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:20:23.821297Repositório 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 |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
title |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
spellingShingle |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions Lapa, Hugo Gold(III) complex C-scorpionate Toluene oxidation Oxidative esterification Value-added product |
title_short |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
title_full |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
title_fullStr |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
title_full_unstemmed |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
title_sort |
C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions |
author |
Lapa, Hugo |
author_facet |
Lapa, Hugo Guedes Da Silva, M. Fátima C. Pombeiro, Armando Alegria, Elisabete Martins, Luisa |
author_role |
author |
author2 |
Guedes Da Silva, M. Fátima C. Pombeiro, Armando Alegria, Elisabete Martins, Luisa |
author2_role |
author author author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Lapa, Hugo Guedes Da Silva, M. Fátima C. Pombeiro, Armando Alegria, Elisabete Martins, Luisa |
dc.subject.por.fl_str_mv |
Gold(III) complex C-scorpionate Toluene oxidation Oxidative esterification Value-added product |
topic |
Gold(III) complex C-scorpionate Toluene oxidation Oxidative esterification Value-added product |
description |
The new Au(III) complex [AuCl2(Tpms)] (1) and the previously reported [AuCl2(Tpm)]Cl (2), bearing the potentially tridentate ligands tris(1-pyrazolyl)methanesulfonate (SO3C(C3H3N2)(3)(-), Tpms) or hydrotris(1-pyrazolyl) methane (HC(C3H3N2)(3), Tpm), respectively, were synthesized in water at room temperature and characterized using NMR and IR spectroscopy. The molecular structure of 1 was authenticated by single crystal X-ray diffraction analysis. The catalytic performance of the Au(III) complexes was tested, for the first time, in toluene and benzyl alcohol oxidation reactions. The oxidative esterification of benzaldehyde, by-product of toluene oxidation, was further explored. In order to optimize the catalytic systems, the influence of parameters such as temperature, reaction time, amount of pre-catalyst and the presence of additives was evaluated. In the peroxidative (by H2O2 or t-BuOOH) oxidation reactions, a maximum total yield (benzylic alcohol and benzaldehyde) of 8% for toluene oxidation with pre-catalyst 1 (6 h, 80 degrees C, H2O2 30% aq. sol.) and a maximum total yield (benzaldehyde and benzoic acid) of 43% for benzyl alcohol oxidation with pre-catalyst 2 (24 h, 80 degrees C, t-BuOOH 70% aq. sol.) with a selectivity of 72% for benzaldehyde, were obtained. The esterification of benzaldehyde yielded, in the presence of 1, a maximum of 27% and 48% of methyl benzoate, at room temperature and 80 degrees C, respectively, and with a selectivity of 78% for methyl benzoate. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-10-06T16:51:00Z 2020-11-01 2020-11-01T00:00:00Z |
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/10400.21/12275 |
url |
http://hdl.handle.net/10400.21/12275 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
LAPA, Hugo M.; [et al] – C-scorpionate Au(III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions. Inorganica Chimica Acta. ISSN 0020-1693. Vol. 512 (2020), pp. 1-11 0020-1693 10.1016/j.ica.2020.119881 |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
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metadata only access |
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 |
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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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