Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II)
Ano de defesa: | 2013 |
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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
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4248 |
Resumo: | Triazenes are a class of compounds characterized by the presence of a diazoamino functional group (N=N N) showing remarkable ability to support the stereochemical requisites of a wide variety of metal transition complexes. They act as versatile ligands in coordination chemistry when deprotonated and have relevant biological and synthetic porperties. This work presents the synthesis and investigation of molecular and crystal structure of a new series of monotriazenes [3-(4-phenyldiazenyl)-1-(2-fluorophenyl)triazene (2b); 1-(2-chlorophenyl)-3-(4-phenyldiazenyl)triazeno (2c), 1-(2-bromophenyl)-3-(4-phenyldiazenyl)triazene (2d); 3-(4-phenyldiazenyl)-1-(2-iodophenyl) triazene (2e); 1,3-bis-(3-methoxy-4-methylbenzoate)triazene (2g)] and substituted 1,4-bis (phenyltriazenyl)butanes, C6H5N(H)=N-N(CH2)4-N=NN(H)C6H5, [1,4-bis(4-ethyl-benzoato triazenyl) butane (5a), 1,4-bis(2-fluorophenyltriazenyl)butane (5b), 1,4-bis(2-clorophenyltriazenyl)butane (5c), 1,4-bis(2-bromophenyltriazenyl)butane (5d), 1,4-bis(2-iodophenyltriazenyl)butane (5e), 1,4-bis(4-amidophenyltriazenyll)butane (5f)]. The insertion of groups on phenyl rings attached to the triazene chains makes the environment significantly more interesting coordination providing the supramolecular array through noncovalent intermolecular interactions and self-organizatinal units of primary molecule. The metal ions used for complexation are salts of Ni2+, Cu2+ and Pd2+ and they were chosen due to the attracting biological relevance, magnetic properties, catalytic yielding. Nine metal complexes unpublished were synthesized [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c) [(PdII (R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl) DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g) [CuII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a), R = F (6b), R = NH2C(O) (6f)], [NiII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b) R = Cl (7c) R = Br (7d) R = NH2C(O) (7f)]. The synthesis and characterization of these compounds is justified by the exploration of the reactivity, the coordinative behavior and by the understanding of the interactions between different ligands and metal centers. The structural analysis of the synthesized compounds by X-ray diffraction on single crystal in the solid state were performed for characterization of interactions in the crystal. Thus, a thorough understanding of the relationship between the crystal structure and supramolecular organization is analyzed. Besides the structural analysis of compounds, elemental analysis CHN, infrared, nuclear magnetic resonance and ultraviolet-visible spectroscopies and mass spectrometry were also carried out for characterization. The physical chemical properties were investigated through thermogravimetric analysis and magnetic susceptibility. |
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2017-05-162017-05-162013-04-30BROCH, Fernanda. Synthesis, crystallography and properties of the mono and bistriazene ligands and its complexes derivatives with Cu(II), Ni(II) and Pd(II). 2013. 239 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/4248Triazenes are a class of compounds characterized by the presence of a diazoamino functional group (N=N N) showing remarkable ability to support the stereochemical requisites of a wide variety of metal transition complexes. They act as versatile ligands in coordination chemistry when deprotonated and have relevant biological and synthetic porperties. This work presents the synthesis and investigation of molecular and crystal structure of a new series of monotriazenes [3-(4-phenyldiazenyl)-1-(2-fluorophenyl)triazene (2b); 1-(2-chlorophenyl)-3-(4-phenyldiazenyl)triazeno (2c), 1-(2-bromophenyl)-3-(4-phenyldiazenyl)triazene (2d); 3-(4-phenyldiazenyl)-1-(2-iodophenyl) triazene (2e); 1,3-bis-(3-methoxy-4-methylbenzoate)triazene (2g)] and substituted 1,4-bis (phenyltriazenyl)butanes, C6H5N(H)=N-N(CH2)4-N=NN(H)C6H5, [1,4-bis(4-ethyl-benzoato triazenyl) butane (5a), 1,4-bis(2-fluorophenyltriazenyl)butane (5b), 1,4-bis(2-clorophenyltriazenyl)butane (5c), 1,4-bis(2-bromophenyltriazenyl)butane (5d), 1,4-bis(2-iodophenyltriazenyl)butane (5e), 1,4-bis(4-amidophenyltriazenyll)butane (5f)]. The insertion of groups on phenyl rings attached to the triazene chains makes the environment significantly more interesting coordination providing the supramolecular array through noncovalent intermolecular interactions and self-organizatinal units of primary molecule. The metal ions used for complexation are salts of Ni2+, Cu2+ and Pd2+ and they were chosen due to the attracting biological relevance, magnetic properties, catalytic yielding. Nine metal complexes unpublished were synthesized [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c) [(PdII (R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl) DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g) [CuII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a), R = F (6b), R = NH2C(O) (6f)], [NiII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b) R = Cl (7c) R = Br (7d) R = NH2C(O) (7f)]. The synthesis and characterization of these compounds is justified by the exploration of the reactivity, the coordinative behavior and by the understanding of the interactions between different ligands and metal centers. The structural analysis of the synthesized compounds by X-ray diffraction on single crystal in the solid state were performed for characterization of interactions in the crystal. Thus, a thorough understanding of the relationship between the crystal structure and supramolecular organization is analyzed. Besides the structural analysis of compounds, elemental analysis CHN, infrared, nuclear magnetic resonance and ultraviolet-visible spectroscopies and mass spectrometry were also carried out for characterization. The physical chemical properties were investigated through thermogravimetric analysis and magnetic susceptibility.Triazenos são importantes membros da família de compostos nitrogenados de cadeia aberta, caracterizados por conter o grupo funcional [N═N─N] e apresentam diferentes propriedades de coordenação a metais de transição. São compostos fracamente ácidos e quando desprotonados atuam como ótimos ligantes na química de coordenação apresentando grande importância sintética e biológica. Nessa tese, foi inicialmente desenvolvida a síntese de uma série inédita de compostos triazenos monocatenados [3-(4-fenildiazenil)-1-(2-fluorofenil)triazeno (2b); 1-(2-clorofenil)-3-(4-fenildiazenil)triazeno (2c); 1-(2-bromofenil)-3-(4-fenildiazenil)triazeno (2d); 3-(4-fenildiazenil)-1-(2-iodofenil)triazeno (2e); 1,3-bis(3-metoxi-4-metilbenzoato)triazeno (2g)] e de compostos triazenos biscatenados derivados do 1,4-bis(feniltriazenido)butano, C6H5N(H)N=N-(CH2)4-N=N-N(H)C6H5, [1,4-bis(etil-4-benzoatotriazenil) butano (5a); 1,4-bis(2-fluorofeniltriazenido)butano (5b); 1,4-bis(2-clorofeniltriazenido)butano (5c); 1,4-bis(2-bromofeniltriazenido)butano (5d); 1,4-bis(2-iodofeniltriazenido)butano (5e); 1,4-bis(4-amidofeniltriazenido)butano (5f)]. A inserção de grupamentos substituintes nos anéis fenila na cadeia triazenídica tornam o ambiente de coordenação significativamente mais interessante, propiciando o aumento da ocorrência de interações intermoleculares não covalentes e impondo a auto-organização de unidades moleculares primárias no estado sólido. Os metais escolhidos para complexação foram sais de Ni2+, Cu2+ e Pd2+ em virtude de atraírem atenção como objeto de estudos relacionados com medicina, propriedades magnéticas e catálise obtendo-se como resultados deste trabalho nove complexos metálicos inéditos [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c); [(PdII(R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl)·DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g); [CuII(RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a); R = F (6b); R = NH2C(O) (6f)] ; [NiII(RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b); R = Cl (7c); R = Br (7d); R = NH2C(O) (7f)]. A síntese, e a caracterização desses novos compostos estão relacionadas à exploração da reatividade, ao comportamento coordenativo e a compreensão das interações entre os diferentes centros metálicos e os ligantes. Efetuou-se um estudo estrutural no estado sólido para a caracterização das interações presentes nas estruturas cristalinas dos compostos sintetizados e a ferramenta utilizada foi à difração de raios X em monocristal. Dessa forma aprofundou-se a compreensão da relação entre a estrutura cristalina e sua organização supramolecular. Além do método de difração de raios X de monocristal os compostos foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, 1H e 13C, espectroscopia ultravioleta e visível, espectrometria de massas e análise elementar CHN. As propriedades físico-químicas foram investigadas através de análise termogravimétrica e susceptibilidade magnética.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaMonotriazenosBistriazenosComplexos binucleares de cobre e níquelPaládioDifração de raios XQuímica supramolecularMonotriazeneBistriazeneBinuclear copper(II) and nickel(II) complexesPaladiumX-ray diffractionSupramolecular chemistryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II)Synthesis, crystallography and properties of the mono and bistriazene ligands and its complexes derivatives with Cu(II), Ni(II) and Pd(II)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisHörner, Manfredohttp://lattes.cnpq.br/8922528250830998Nunes, Fabio Souzahttp://lattes.cnpq.br/7117607785614286Casagrande Junior, Osvaldo de Lazarohttp://lattes.cnpq.br/3607137600981861Bresolin, Leandrohttp://lattes.cnpq.br/3961672079507969Squizani, Fatimahttp://lattes.cnpq.br/1060502818943139http://lattes.cnpq.br/4916197985145809Broch, Fernanda1006000000004003003003003003003007e7796b1-053d-4bbe-8e62-e769f0da5ceaf1769b0d-0060-42c9-82c0-8819ed0e30f03694402e-84bf-43d1-a3a8-562172c52655e3814618-6623-47f2-aa82-43758306c30f67ed52a8-91fa-4e1a-b8bb-f266fe5782cec8d82e44-e756-4176-b4e9-14958419c324info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALBROCH, FERNANDA.pdfapplication/pdf9370105http://repositorio.ufsm.br/bitstream/1/4248/1/BROCH%2c%20FERNANDA.pdf02c020364643f1067754414777e6930eMD51TEXTBROCH, FERNANDA.pdf.txtBROCH, FERNANDA.pdf.txtExtracted texttext/plain378543http://repositorio.ufsm.br/bitstream/1/4248/2/BROCH%2c%20FERNANDA.pdf.txt2720b6bbba797571c1323f537931f1e3MD52THUMBNAILBROCH, FERNANDA.pdf.jpgBROCH, FERNANDA.pdf.jpgIM Thumbnailimage/jpeg5639http://repositorio.ufsm.br/bitstream/1/4248/3/BROCH%2c%20FERNANDA.pdf.jpg6c991f432fb47edf90e2ec803470ed34MD531/42482023-05-12 11:18:10.718oai:repositorio.ufsm.br:1/4248Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132023-05-12T14:18:10Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
dc.title.alternative.eng.fl_str_mv |
Synthesis, crystallography and properties of the mono and bistriazene ligands and its complexes derivatives with Cu(II), Ni(II) and Pd(II) |
title |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
spellingShingle |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) Broch, Fernanda Monotriazenos Bistriazenos Complexos binucleares de cobre e níquel Paládio Difração de raios X Química supramolecular Monotriazene Bistriazene Binuclear copper(II) and nickel(II) complexes Paladium X-ray diffraction Supramolecular chemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
title_full |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
title_fullStr |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
title_full_unstemmed |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
title_sort |
Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II) |
author |
Broch, Fernanda |
author_facet |
Broch, Fernanda |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Hörner, Manfredo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/8922528250830998 |
dc.contributor.referee1.fl_str_mv |
Nunes, Fabio Souza |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/7117607785614286 |
dc.contributor.referee2.fl_str_mv |
Casagrande Junior, Osvaldo de Lazaro |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/3607137600981861 |
dc.contributor.referee3.fl_str_mv |
Bresolin, Leandro |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/3961672079507969 |
dc.contributor.referee4.fl_str_mv |
Squizani, Fatima |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/1060502818943139 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4916197985145809 |
dc.contributor.author.fl_str_mv |
Broch, Fernanda |
contributor_str_mv |
Hörner, Manfredo Nunes, Fabio Souza Casagrande Junior, Osvaldo de Lazaro Bresolin, Leandro Squizani, Fatima |
dc.subject.por.fl_str_mv |
Monotriazenos Bistriazenos Complexos binucleares de cobre e níquel Paládio Difração de raios X Química supramolecular |
topic |
Monotriazenos Bistriazenos Complexos binucleares de cobre e níquel Paládio Difração de raios X Química supramolecular Monotriazene Bistriazene Binuclear copper(II) and nickel(II) complexes Paladium X-ray diffraction Supramolecular chemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Monotriazene Bistriazene Binuclear copper(II) and nickel(II) complexes Paladium X-ray diffraction Supramolecular chemistry |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Triazenes are a class of compounds characterized by the presence of a diazoamino functional group (N=N N) showing remarkable ability to support the stereochemical requisites of a wide variety of metal transition complexes. They act as versatile ligands in coordination chemistry when deprotonated and have relevant biological and synthetic porperties. This work presents the synthesis and investigation of molecular and crystal structure of a new series of monotriazenes [3-(4-phenyldiazenyl)-1-(2-fluorophenyl)triazene (2b); 1-(2-chlorophenyl)-3-(4-phenyldiazenyl)triazeno (2c), 1-(2-bromophenyl)-3-(4-phenyldiazenyl)triazene (2d); 3-(4-phenyldiazenyl)-1-(2-iodophenyl) triazene (2e); 1,3-bis-(3-methoxy-4-methylbenzoate)triazene (2g)] and substituted 1,4-bis (phenyltriazenyl)butanes, C6H5N(H)=N-N(CH2)4-N=NN(H)C6H5, [1,4-bis(4-ethyl-benzoato triazenyl) butane (5a), 1,4-bis(2-fluorophenyltriazenyl)butane (5b), 1,4-bis(2-clorophenyltriazenyl)butane (5c), 1,4-bis(2-bromophenyltriazenyl)butane (5d), 1,4-bis(2-iodophenyltriazenyl)butane (5e), 1,4-bis(4-amidophenyltriazenyll)butane (5f)]. The insertion of groups on phenyl rings attached to the triazene chains makes the environment significantly more interesting coordination providing the supramolecular array through noncovalent intermolecular interactions and self-organizatinal units of primary molecule. The metal ions used for complexation are salts of Ni2+, Cu2+ and Pd2+ and they were chosen due to the attracting biological relevance, magnetic properties, catalytic yielding. Nine metal complexes unpublished were synthesized [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c) [(PdII (R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl) DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g) [CuII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a), R = F (6b), R = NH2C(O) (6f)], [NiII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b) R = Cl (7c) R = Br (7d) R = NH2C(O) (7f)]. The synthesis and characterization of these compounds is justified by the exploration of the reactivity, the coordinative behavior and by the understanding of the interactions between different ligands and metal centers. The structural analysis of the synthesized compounds by X-ray diffraction on single crystal in the solid state were performed for characterization of interactions in the crystal. Thus, a thorough understanding of the relationship between the crystal structure and supramolecular organization is analyzed. Besides the structural analysis of compounds, elemental analysis CHN, infrared, nuclear magnetic resonance and ultraviolet-visible spectroscopies and mass spectrometry were also carried out for characterization. The physical chemical properties were investigated through thermogravimetric analysis and magnetic susceptibility. |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-04-30 |
dc.date.accessioned.fl_str_mv |
2017-05-16 |
dc.date.available.fl_str_mv |
2017-05-16 |
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info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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dc.identifier.citation.fl_str_mv |
BROCH, Fernanda. Synthesis, crystallography and properties of the mono and bistriazene ligands and its complexes derivatives with Cu(II), Ni(II) and Pd(II). 2013. 239 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4248 |
identifier_str_mv |
BROCH, Fernanda. Synthesis, crystallography and properties of the mono and bistriazene ligands and its complexes derivatives with Cu(II), Ni(II) and Pd(II). 2013. 239 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/4248 |
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