Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural
Ano de defesa: | 2020 |
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Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
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País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/23271 |
Resumo: | This work describes the synthesis and characterization of eleven new palladium compounds with formula [Pd3(-SeMes)4(bipy)2](PF6)2·2MeCN (1), [Pd3(-SePh)4(bipy)2](PF6)2·bipy (2), [Pd2(- SePh)2(bipy)2](PF6)2 (3), [Pd2(-SeC6H4Cl-p)2(bipy)2](PF6)2 (4), [Pd3(3-Se)2(bipy)3](PF6)2∙5THF (5), [Pd2(-SeC6H4F-p)2(bipy)2](PF6)2 (6), [Pd3(-TeMes)4(bipy)2](PF6)2 (7), [Pd2(-TePh)2(bipy)2](PF6)2 (8), [Pd2(-TeC6H4 tBu-p)2(bipy)2](PF6)2∙DMF (9), [Pd2(-TeC6H4F-p)2(bipy)2](PF6)2 (10) e [PdI(TePyo)( I2TePy-o)2] (11), based on diaryldichalcogenides containing electron donating (EDG) or electron withdrawing groups (EWG). Compounds 1 – 10 have intramolecular Pd∙∙∙Pd interactions which vary according to the structural conformation promoted by different (EAr)2 used. Only compound 9 has intermolecular Pd∙∙∙Pd interactions, which are shorter when compared to its intramolecular Pd ∙∙∙ Pd. Six of these compounds derive from selenium and five of these derive from tellurium and all of it were characterized by X ray diffraction, besides elemental analysis, infrared spectroscopy, mass spectrometry and nuclear magnetic resonance spectroscopy 77Se, 125Te (NMR). The methodologies used to get compounds 1 – 11 were basically oxidative addition (1, 5, 7, 8, 9 e 10) and ligand substitution (2, 3, 4 e 6). On the other hand, compound 11 was obtained through elemental palladium oxidation by a diiodine adduct of (o-PyTe)2 generated in situ during the reaction. The use of (ArE)2 containing EDG and EWG resulted in structures with different nuclearities, conformations and nuclearities, conformations and coordination environments. The generated equilibrium in solution for compound 3 was determined by 1H, 13C and 77Se, where the 2D spectra (COSY, HSQC and HMBC) were carried out to assign proton and carbon signals corresponding to its chemical shifts from the structures in equilibrium. The mass spectrum for compound 3 shows the signals related to the fragments of the two species in equilibrium (3 and 3 'determined by NMR), confirming the NMR data interpreted. DFT calculations were carried out for compound 11 and the results suggest delocalized electrons (aromaticity) in its five-membered rings. These delocalized electrons in the system homogenize the oxidation states of the different tellurium species, [I2TePy-o]- and [TePy-o]+, in the structure of 11. |
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2021-12-13T17:27:25Z2021-12-13T17:27:25Z2020-02-17http://repositorio.ufsm.br/handle/1/23271This work describes the synthesis and characterization of eleven new palladium compounds with formula [Pd3(-SeMes)4(bipy)2](PF6)2·2MeCN (1), [Pd3(-SePh)4(bipy)2](PF6)2·bipy (2), [Pd2(- SePh)2(bipy)2](PF6)2 (3), [Pd2(-SeC6H4Cl-p)2(bipy)2](PF6)2 (4), [Pd3(3-Se)2(bipy)3](PF6)2∙5THF (5), [Pd2(-SeC6H4F-p)2(bipy)2](PF6)2 (6), [Pd3(-TeMes)4(bipy)2](PF6)2 (7), [Pd2(-TePh)2(bipy)2](PF6)2 (8), [Pd2(-TeC6H4 tBu-p)2(bipy)2](PF6)2∙DMF (9), [Pd2(-TeC6H4F-p)2(bipy)2](PF6)2 (10) e [PdI(TePyo)( I2TePy-o)2] (11), based on diaryldichalcogenides containing electron donating (EDG) or electron withdrawing groups (EWG). Compounds 1 – 10 have intramolecular Pd∙∙∙Pd interactions which vary according to the structural conformation promoted by different (EAr)2 used. Only compound 9 has intermolecular Pd∙∙∙Pd interactions, which are shorter when compared to its intramolecular Pd ∙∙∙ Pd. Six of these compounds derive from selenium and five of these derive from tellurium and all of it were characterized by X ray diffraction, besides elemental analysis, infrared spectroscopy, mass spectrometry and nuclear magnetic resonance spectroscopy 77Se, 125Te (NMR). The methodologies used to get compounds 1 – 11 were basically oxidative addition (1, 5, 7, 8, 9 e 10) and ligand substitution (2, 3, 4 e 6). On the other hand, compound 11 was obtained through elemental palladium oxidation by a diiodine adduct of (o-PyTe)2 generated in situ during the reaction. The use of (ArE)2 containing EDG and EWG resulted in structures with different nuclearities, conformations and nuclearities, conformations and coordination environments. The generated equilibrium in solution for compound 3 was determined by 1H, 13C and 77Se, where the 2D spectra (COSY, HSQC and HMBC) were carried out to assign proton and carbon signals corresponding to its chemical shifts from the structures in equilibrium. The mass spectrum for compound 3 shows the signals related to the fragments of the two species in equilibrium (3 and 3 'determined by NMR), confirming the NMR data interpreted. DFT calculations were carried out for compound 11 and the results suggest delocalized electrons (aromaticity) in its five-membered rings. These delocalized electrons in the system homogenize the oxidation states of the different tellurium species, [I2TePy-o]- and [TePy-o]+, in the structure of 11.Este trabalho descreve a síntese e caracterização estrutural de onze novos compostos de paládio de fórmula [Pd3(-SeMes)4(bipy)2](PF6)2·2MeCN (1), [Pd3(-SePh)4(bipy)2](PF6)2·bipy (2), [Pd2(- SePh)2(bipy)2](PF6)2 (3), [Pd2(-SeC6H4Cl-p)2(bipy)2](PF6)2 (4), [Pd3(3-Se)2(bipy)3](PF6)2∙5THF (5), [Pd2(-SeC6H4F-p)2(bipy)2](PF6)2 (6), [Pd3(-TeMes)4(bipy)2](PF6)2 (7), [Pd2(-TePh)2(bipy)2](PF6)2 (8), [Pd2(-TeC6H4 tBu-p)2(bipy)2](PF6)2∙DMF (9), [Pd2(-TeC6H4F-p)2(bipy)2](PF6)2 (10) e [PdI(TePyo)( I2TePy-o)2] (11), derivados de dicalcogenetos de diarila contendo substituintes doadores (EDG) ou retiradores de elétrons (EWG). As estruturas dos compostos 1 – 10 possuem interações intramoleculares Pd∙∙∙Pd, as quais variam de acordo com a conformação estrutural promovida pelo uso de diferentes (EAr)2. Somente o composto 9 possui interações Pd∙∙∙Pd intermoleculares, as quais são mais curtas quando comparadas às Pd∙∙∙Pd intramoleculares do mesmo composto. Dos onze resultados obtidos, seis derivam de selênio e cinco de telúrio e todos foram caracterizados por difração de raios X em monocristal, além de análise elementar, espectroscopia vibracional na região do infravermelho, espectrometria de massas e espectroscopia de ressonância magnética nuclear (RMN) de 77Se e 125Te. As metodologias empregadas para obtenção dos produtos 1 – 10 foram basicamente adição oxidativa (1, 5, 7, 8, 9 e 10) e substituição de ligantes (2, 3, 4 e 6). Já o composto 11 foi obtido pela oxidação de Pd elementar por um aduto diiodado derivado do (o-PyTe)2 gerado in situ na reação. O emprego de diferentes pré-ligantes (ArE)2 contendo EDG e EWG resultou na geração dos produtos com diferentes nuclearidades, conformações, modos e ambientes de coordenação. O equilíbrio gerado em solução para o composto 3 foi determinado por RMN de 1H, 13C e 77Se, onde os espectros 2D (COSY, HSQC e HMBC) foram realizados para atribuição dos sinais dos prótons e carbonos correspondentes aos deslocamentos químicos das estruturas em equilíbrio. O espectro de massas para o composto 3 possui os sinais das duas espécies em equilíbrio (3 e 3’ determinadas por RMN), corroborando os dados interpretados por RMN. Cálculos de DFT foram realizados para o composto 11 e os resultados sugerem deslocalização eletrônica (aromaticidade) nos anéis de cinco membros deste composto. Essa deslocalização eletrônica no sistema homogeneíza os estados de oxidação das diferentes espécies de telúrio, [I2TePy-o]- e [TePy-o]+, na estrutura do composto 11.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessPaládioDicalcogenetos de diarilaTelúrioSelênioInterações Pd∙∙∙PdEquilíbrioRMNDeslocalização eletrônicaPalladiumDiaryl dichalcogenidesTelluriumSeleniumPd∙∙∙Pd interactionsEquilibriumNMRElectronic delocationCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICACalcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estruturalPalladium chalcogenides and chalcogenolates (Se, Te): synthesis and structural characterizationinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisLang, Ernesto Schulzhttp://lattes.cnpq.br/4481982189769819Tirloni, BárbaraPinheiro, Adriana CastroBack, Davi FernandoNakagaki, ShirleySchwade, Vânia Denisehttp://lattes.cnpq.br/2263468025844725Cechin, Camila Nunes1006000000006006006006006006000c9d7568-d5c4-466d-b807-0125a7d37b9746db7329-853a-4e62-bbb2-fd908063c19ca6258a1c-3b1b-4b10-8de8-da9ca27f8440d2affe14-de5b-4ab6-afc3-66619292d6f5f33f5bf0-5193-4fac-992b-192381823da8ed641ce8-22d0-4114-a7a1-e5e9c6d4dbe48215c2bd-7422-406d-8eb0-8b40693ffc39reponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2020_CECHIN_CAMILA.pdfDIS_PPGQUIMICA_2020_CECHIN_CAMILA.pdfDissertação de Mestradoapplication/pdf8945264http://repositorio.ufsm.br/bitstream/1/23271/1/DIS_PPGQUIMICA_2020_CECHIN_CAMILA.pdf88ab2438bbf8847a24cc789bfb36b037MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
dc.title.alternative.eng.fl_str_mv |
Palladium chalcogenides and chalcogenolates (Se, Te): synthesis and structural characterization |
title |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
spellingShingle |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural Cechin, Camila Nunes Paládio Dicalcogenetos de diarila Telúrio Selênio Interações Pd∙∙∙Pd Equilíbrio RMN Deslocalização eletrônica Palladium Diaryl dichalcogenides Tellurium Selenium Pd∙∙∙Pd interactions Equilibrium NMR Electronic delocation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
title_full |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
title_fullStr |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
title_full_unstemmed |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
title_sort |
Calcogenetos e calcogenolatos (Se, Te) de paládio: síntese e caracterização estrutural |
author |
Cechin, Camila Nunes |
author_facet |
Cechin, Camila Nunes |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Lang, Ernesto Schulz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/4481982189769819 |
dc.contributor.advisor-co1.fl_str_mv |
Tirloni, Bárbara |
dc.contributor.referee1.fl_str_mv |
Pinheiro, Adriana Castro |
dc.contributor.referee2.fl_str_mv |
Back, Davi Fernando |
dc.contributor.referee3.fl_str_mv |
Nakagaki, Shirley |
dc.contributor.referee4.fl_str_mv |
Schwade, Vânia Denise |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2263468025844725 |
dc.contributor.author.fl_str_mv |
Cechin, Camila Nunes |
contributor_str_mv |
Lang, Ernesto Schulz Tirloni, Bárbara Pinheiro, Adriana Castro Back, Davi Fernando Nakagaki, Shirley Schwade, Vânia Denise |
dc.subject.por.fl_str_mv |
Paládio Dicalcogenetos de diarila Telúrio Selênio Interações Pd∙∙∙Pd Equilíbrio RMN Deslocalização eletrônica |
topic |
Paládio Dicalcogenetos de diarila Telúrio Selênio Interações Pd∙∙∙Pd Equilíbrio RMN Deslocalização eletrônica Palladium Diaryl dichalcogenides Tellurium Selenium Pd∙∙∙Pd interactions Equilibrium NMR Electronic delocation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Palladium Diaryl dichalcogenides Tellurium Selenium Pd∙∙∙Pd interactions Equilibrium NMR Electronic delocation |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes the synthesis and characterization of eleven new palladium compounds with formula [Pd3(-SeMes)4(bipy)2](PF6)2·2MeCN (1), [Pd3(-SePh)4(bipy)2](PF6)2·bipy (2), [Pd2(- SePh)2(bipy)2](PF6)2 (3), [Pd2(-SeC6H4Cl-p)2(bipy)2](PF6)2 (4), [Pd3(3-Se)2(bipy)3](PF6)2∙5THF (5), [Pd2(-SeC6H4F-p)2(bipy)2](PF6)2 (6), [Pd3(-TeMes)4(bipy)2](PF6)2 (7), [Pd2(-TePh)2(bipy)2](PF6)2 (8), [Pd2(-TeC6H4 tBu-p)2(bipy)2](PF6)2∙DMF (9), [Pd2(-TeC6H4F-p)2(bipy)2](PF6)2 (10) e [PdI(TePyo)( I2TePy-o)2] (11), based on diaryldichalcogenides containing electron donating (EDG) or electron withdrawing groups (EWG). Compounds 1 – 10 have intramolecular Pd∙∙∙Pd interactions which vary according to the structural conformation promoted by different (EAr)2 used. Only compound 9 has intermolecular Pd∙∙∙Pd interactions, which are shorter when compared to its intramolecular Pd ∙∙∙ Pd. Six of these compounds derive from selenium and five of these derive from tellurium and all of it were characterized by X ray diffraction, besides elemental analysis, infrared spectroscopy, mass spectrometry and nuclear magnetic resonance spectroscopy 77Se, 125Te (NMR). The methodologies used to get compounds 1 – 11 were basically oxidative addition (1, 5, 7, 8, 9 e 10) and ligand substitution (2, 3, 4 e 6). On the other hand, compound 11 was obtained through elemental palladium oxidation by a diiodine adduct of (o-PyTe)2 generated in situ during the reaction. The use of (ArE)2 containing EDG and EWG resulted in structures with different nuclearities, conformations and nuclearities, conformations and coordination environments. The generated equilibrium in solution for compound 3 was determined by 1H, 13C and 77Se, where the 2D spectra (COSY, HSQC and HMBC) were carried out to assign proton and carbon signals corresponding to its chemical shifts from the structures in equilibrium. The mass spectrum for compound 3 shows the signals related to the fragments of the two species in equilibrium (3 and 3 'determined by NMR), confirming the NMR data interpreted. DFT calculations were carried out for compound 11 and the results suggest delocalized electrons (aromaticity) in its five-membered rings. These delocalized electrons in the system homogenize the oxidation states of the different tellurium species, [I2TePy-o]- and [TePy-o]+, in the structure of 11. |
publishDate |
2020 |
dc.date.issued.fl_str_mv |
2020-02-17 |
dc.date.accessioned.fl_str_mv |
2021-12-13T17:27:25Z |
dc.date.available.fl_str_mv |
2021-12-13T17:27:25Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/23271 |
url |
http://repositorio.ufsm.br/handle/1/23271 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 600 |
dc.relation.authority.fl_str_mv |
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Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
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Programa de Pós-Graduação em Química |
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UFSM |
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Brasil |
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Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
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