Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados

Detalhes bibliográficos
Autor(a) principal: Dias, Isac Marinho
Data de Publicação: 2019
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UFRRJ
Texto Completo: https://rima.ufrrj.br/jspui/handle/20.500.14407/14604
Resumo: Heterociclos aromáticos como os pirazóis são amplamente utilizados na construção de novas arquiteturas moleculares quando coordenados a íons do bloco d, levando a interessantes propriedades biológicas e tecnológicas. Desta forma, o presente trabalho visou a síntese e a caracterização de dois pré-ligantes pirazólicos funcionalizados: 5-amino-1-(benzotiazol-2-il)- 1H-pirazol-4-carboxilato de potássio (L1) e 5-amino-1-(pirazin-2-il)-1H-pirazol-4-carboxilato de potássio (L2). Para a formação de cada pré-ligante foram realizadas três etapas reacionais, a saber: (1) formação do núcleo pirazólico funcionalizado com um grupamento éster, (2) hidrólise e (3) uma etapa de neutralização. Além disto, foi realizada a síntese de um terceiro ligante inédito, contendo contém o grupamento fotossensível azo (-N=N-), (E)-diazeno-1,2-diilbis(4,1- fenileno)bis(hidrazinocarboxilato), chamado de L3. A síntese deste composto foi realizada através da redução do 4-nitrofenol em meio básico para a formação do grupamento azo, seguida de duas reações envolvendo adições à carbonila. Todas as etapas reacionais para a formação dos compostos L1-L3 foram devidamente caracterizadas por espectroscopias na região do infravermelho, RMN 1H e RMN 13C, além de análises como ponto de fusão e CG-MS. Após a formação dos pré-ligantes L1 e L2, estes foram utilizados na síntese de novos compostos de coordenação contendo os íons de CoII, FeII, MnII , CuII e NiII. Através da metodologia de difusão lenta foram obtidas duas novas famílias de compostos de coordenação cuja fórmula molecular é cis-[M(L1)2(OH2)4] (M= FeII, CoII e NiII) e trans-[M(L2)2(OH2)4] (MnII e CoII). A estruturas cristalinas destes complexos foram elucidadas por difração de raios X por monocristal, verificando-se que ligante se coordenou de forma monodentada e que a esfera de coordenação do íon metálico foi completada por quatro moléculas de água. Foi verificado que os retículos cristalinos destes sistemas são estabilizados por ligações de hidrogênio intra e intermoleculares. Os complexos da família cis-[M(L1)2(OH2)4 ainda foram estudados por voltametria cíclica onde foram observados picos de oxidação e redução referentes aos íons de FeII, CoII e NiII . A espectroscopia Mössbauer para o complexo cis-[Fe(L1)2(OH2)4] evidenciou o estado alto spin para o íon FeII no intervalo de temperatura de 4-300 K. As medidas magnéticas para os compostos cis-[Fe(L1)2(OH2)4] (M=CoII e FeII) mostraram um comportamento oriundo da anisotropia magnética axial e rômbica para estes sistemas, uma vez que as interações de troca são desprezíveis devido à grande distância entre os sítios metálicos no empacotamento cristalino. A resposta frente à inibição da enzima acetilcolinesterase dos complexos da família cis-[M(L1)2(OH2)4] revelou taxas de inibição entre 35 - 55% na concentração de 10 μmol L-1 . Utilizando a metodologia de difusão de vapor foram obtidos compostos de coordenação inéditos [Cu(L1)2(Py)2] e [Co(L1)2(Py)2]. Estes compostos também tiveram sua estrutura elucidada por difração de raios X por monocristal, sendo verificado que o complexo [Co(L1)2(Py)2] possui uma geometria tetraédrica distorcida onde o centro metálico e está coordenado a duas moléculas de piridina e dois átomos de grupos carboxilato de ligantes diferentes na forma monodentada. O complexo [Cu(L1)2(Py)2] possui um íon de CuII em uma geometria octaédrica distorcida, verificando-se a coordenação de dois ligantes L1 e duas moléculas de piridina.
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spelling Dias, Isac MarinhoGuedes, Guilherme Pereira1072583605352186http://lattes.cnpq.br/1072583605352186Neves, Amanda Porto Neves7460226353493536http://lattes.cnpq.br/7460226353493536Vaz, Maria das Graças Fialho3903204691885345http://lattes.cnpq.br/39032046918853451169302677565127http://lattes.cnpq.br/11693026775651272023-12-22T03:03:25Z2023-12-22T03:03:25Z2019-03-13DIAS, Isac Marinho. Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados. 2019. 170f. Dissertação (Mestrado em Química, Química Inorgânica). Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, RJ, 2019.https://rima.ufrrj.br/jspui/handle/20.500.14407/14604Heterociclos aromáticos como os pirazóis são amplamente utilizados na construção de novas arquiteturas moleculares quando coordenados a íons do bloco d, levando a interessantes propriedades biológicas e tecnológicas. Desta forma, o presente trabalho visou a síntese e a caracterização de dois pré-ligantes pirazólicos funcionalizados: 5-amino-1-(benzotiazol-2-il)- 1H-pirazol-4-carboxilato de potássio (L1) e 5-amino-1-(pirazin-2-il)-1H-pirazol-4-carboxilato de potássio (L2). Para a formação de cada pré-ligante foram realizadas três etapas reacionais, a saber: (1) formação do núcleo pirazólico funcionalizado com um grupamento éster, (2) hidrólise e (3) uma etapa de neutralização. Além disto, foi realizada a síntese de um terceiro ligante inédito, contendo contém o grupamento fotossensível azo (-N=N-), (E)-diazeno-1,2-diilbis(4,1- fenileno)bis(hidrazinocarboxilato), chamado de L3. A síntese deste composto foi realizada através da redução do 4-nitrofenol em meio básico para a formação do grupamento azo, seguida de duas reações envolvendo adições à carbonila. Todas as etapas reacionais para a formação dos compostos L1-L3 foram devidamente caracterizadas por espectroscopias na região do infravermelho, RMN 1H e RMN 13C, além de análises como ponto de fusão e CG-MS. Após a formação dos pré-ligantes L1 e L2, estes foram utilizados na síntese de novos compostos de coordenação contendo os íons de CoII, FeII, MnII , CuII e NiII. Através da metodologia de difusão lenta foram obtidas duas novas famílias de compostos de coordenação cuja fórmula molecular é cis-[M(L1)2(OH2)4] (M= FeII, CoII e NiII) e trans-[M(L2)2(OH2)4] (MnII e CoII). A estruturas cristalinas destes complexos foram elucidadas por difração de raios X por monocristal, verificando-se que ligante se coordenou de forma monodentada e que a esfera de coordenação do íon metálico foi completada por quatro moléculas de água. Foi verificado que os retículos cristalinos destes sistemas são estabilizados por ligações de hidrogênio intra e intermoleculares. Os complexos da família cis-[M(L1)2(OH2)4 ainda foram estudados por voltametria cíclica onde foram observados picos de oxidação e redução referentes aos íons de FeII, CoII e NiII . A espectroscopia Mössbauer para o complexo cis-[Fe(L1)2(OH2)4] evidenciou o estado alto spin para o íon FeII no intervalo de temperatura de 4-300 K. As medidas magnéticas para os compostos cis-[Fe(L1)2(OH2)4] (M=CoII e FeII) mostraram um comportamento oriundo da anisotropia magnética axial e rômbica para estes sistemas, uma vez que as interações de troca são desprezíveis devido à grande distância entre os sítios metálicos no empacotamento cristalino. A resposta frente à inibição da enzima acetilcolinesterase dos complexos da família cis-[M(L1)2(OH2)4] revelou taxas de inibição entre 35 - 55% na concentração de 10 μmol L-1 . Utilizando a metodologia de difusão de vapor foram obtidos compostos de coordenação inéditos [Cu(L1)2(Py)2] e [Co(L1)2(Py)2]. Estes compostos também tiveram sua estrutura elucidada por difração de raios X por monocristal, sendo verificado que o complexo [Co(L1)2(Py)2] possui uma geometria tetraédrica distorcida onde o centro metálico e está coordenado a duas moléculas de piridina e dois átomos de grupos carboxilato de ligantes diferentes na forma monodentada. O complexo [Cu(L1)2(Py)2] possui um íon de CuII em uma geometria octaédrica distorcida, verificando-se a coordenação de dois ligantes L1 e duas moléculas de piridina.CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorAromatic heterocycles such as pyrazoles are widely used in the construction of new molecular architectures when coordinated to ions of the d block leading to interesting biological and technological properties. In this work we describe the synthesis and characterization of two functionalized pyrazole ligands: potassium 5-amino-1-(benzothiazol-2-yl)-1H-pyrazole-4-carboxylate (L1) and potassium 5-amino-1-(pyrazin-2-yl)-1H-pyrazole-4-carboxylate (L2). The syntheses of the ligands were performed in three steps: (1) formation of the pyrazole nucleus with an ester group, (2) hydrolysis and (3) neutralization. In addition, a new azo (N=N-) photosensitive compound (E)-diazene-1,2-diylbis(4,1 phenylene)bis(hydrazinecarboxylate) (L3) was obtained. The synthesis of L3 was performed by reduction of 4-nitrophenol in alkaline conditions, affording the azo group, followed by two additions reactions in the phenol and carbonyl groups. All reactions steps were characterized by infrared, 1H-NMR and 13C-NMR spectroscopies, as well as melting point and GC-MS analyzes. The L1 and L2 ligands were used to synthesize new coordination compounds containing CoII, FeII, MnII, CuII and NiII ions. By using the slow diffusion methodology, two new families of coordination compounds wereobtained, with molecular formulas cis-[M(L1)2(OH2)4] (M= FeII, CoII and NiII) and trans-[M(L2)2(OH2)4] (MnII and CoII). The crystal structures of these complexes were solved by X ray diffraction and it was observed that the ligands are coordinated in a monodentate fashion. The crystal packing of these systems is stabilized by intra and intermolecular hydrogen bonds. The complexes cis-[M(L1)2(OH2)4] were studied by cyclic voltammetry, which theoxidation and reduction peaks were observed with respect to the FeII, CoII and NiII ions. The Mössbauer spectroscopy for cis-[Fe(L1)2(OH2)4] showed a high spin state for the FeII ion in the emperature range 4-300 K. The magnetic measurements for the compounds cis-[Fe(L1)2(OH2)4] (M = CoII, FeII) showed a key role played by the axial and rhombic anisotropy from the metal ion, since the exchange interactions are negligible. Furthermore, this family was evaluated against the inhibition of the acetylcholinesterase showing good inhibition rates in aconcentration of 10 μmol L-1. Through the slow diffusion methodology, new coordination compounds [Cu(L1)2(Py)2] and [Co(L1)2(Py)2] were obtained. The crystal structures of the compounds were elucidated by single crystal X-ray diffraction; in the [Co(L1)2(Py)2] complex, the metal ion lies on a distorted tetrahedral geometry, coordinated to two pyridine molecules and two oxygen atoms from different carboxylate groups in a monodentate fashion. The complex [Cu(L1)2(Py)2] presented the CuII ion in a distorted octahedral geometry, with two L1 ligands coordinated in a bidentate fashion the coordination sphere of the metal ion was completed by two coordinated pyridine molecules.application/pdfporUniversidade Federal Rural do Rio de JaneiroPrograma de Pós-Graduação em QuímicaUFRRJBrasilInstituto de QuímicaCompostos de coordenaçãoEstrutura cristalinaPirazolAcetilcolinesteraseAnisotropiaCoordination compoundsCrystal packingPyrazoleAcetylcholinesteraseAnisotropy.QuímicaSíntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizadosSynthesis and characterization of new coordination compounds containing functionalized pyrazole ligandsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisJournal of Molecular Structure 1178 (2019) 155e161, p. 155e161. ABD-ALLAH ZORDOK, W. et al. 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dc.title.por.fl_str_mv Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
dc.title.alternative.eng.fl_str_mv Synthesis and characterization of new coordination compounds containing functionalized pyrazole ligands
title Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
spellingShingle Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
Dias, Isac Marinho
Compostos de coordenação
Estrutura cristalina
Pirazol
Acetilcolinesterase
Anisotropia
Coordination compounds
Crystal packing
Pyrazole
Acetylcholinesterase
Anisotropy.
Química
title_short Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
title_full Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
title_fullStr Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
title_full_unstemmed Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
title_sort Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados
author Dias, Isac Marinho
author_facet Dias, Isac Marinho
author_role author
dc.contributor.author.fl_str_mv Dias, Isac Marinho
dc.contributor.advisor1.fl_str_mv Guedes, Guilherme Pereira
dc.contributor.advisor1ID.fl_str_mv 1072583605352186
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/1072583605352186
dc.contributor.referee1.fl_str_mv Neves, Amanda Porto Neves
dc.contributor.referee1ID.fl_str_mv 7460226353493536
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/7460226353493536
dc.contributor.referee2.fl_str_mv Vaz, Maria das Graças Fialho
dc.contributor.referee2ID.fl_str_mv 3903204691885345
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/3903204691885345
dc.contributor.authorID.fl_str_mv 1169302677565127
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/1169302677565127
contributor_str_mv Guedes, Guilherme Pereira
Neves, Amanda Porto Neves
Vaz, Maria das Graças Fialho
dc.subject.por.fl_str_mv Compostos de coordenação
Estrutura cristalina
Pirazol
Acetilcolinesterase
Anisotropia
topic Compostos de coordenação
Estrutura cristalina
Pirazol
Acetilcolinesterase
Anisotropia
Coordination compounds
Crystal packing
Pyrazole
Acetylcholinesterase
Anisotropy.
Química
dc.subject.eng.fl_str_mv Coordination compounds
Crystal packing
Pyrazole
Acetylcholinesterase
Anisotropy.
dc.subject.cnpq.fl_str_mv Química
description Heterociclos aromáticos como os pirazóis são amplamente utilizados na construção de novas arquiteturas moleculares quando coordenados a íons do bloco d, levando a interessantes propriedades biológicas e tecnológicas. Desta forma, o presente trabalho visou a síntese e a caracterização de dois pré-ligantes pirazólicos funcionalizados: 5-amino-1-(benzotiazol-2-il)- 1H-pirazol-4-carboxilato de potássio (L1) e 5-amino-1-(pirazin-2-il)-1H-pirazol-4-carboxilato de potássio (L2). Para a formação de cada pré-ligante foram realizadas três etapas reacionais, a saber: (1) formação do núcleo pirazólico funcionalizado com um grupamento éster, (2) hidrólise e (3) uma etapa de neutralização. Além disto, foi realizada a síntese de um terceiro ligante inédito, contendo contém o grupamento fotossensível azo (-N=N-), (E)-diazeno-1,2-diilbis(4,1- fenileno)bis(hidrazinocarboxilato), chamado de L3. A síntese deste composto foi realizada através da redução do 4-nitrofenol em meio básico para a formação do grupamento azo, seguida de duas reações envolvendo adições à carbonila. Todas as etapas reacionais para a formação dos compostos L1-L3 foram devidamente caracterizadas por espectroscopias na região do infravermelho, RMN 1H e RMN 13C, além de análises como ponto de fusão e CG-MS. Após a formação dos pré-ligantes L1 e L2, estes foram utilizados na síntese de novos compostos de coordenação contendo os íons de CoII, FeII, MnII , CuII e NiII. Através da metodologia de difusão lenta foram obtidas duas novas famílias de compostos de coordenação cuja fórmula molecular é cis-[M(L1)2(OH2)4] (M= FeII, CoII e NiII) e trans-[M(L2)2(OH2)4] (MnII e CoII). A estruturas cristalinas destes complexos foram elucidadas por difração de raios X por monocristal, verificando-se que ligante se coordenou de forma monodentada e que a esfera de coordenação do íon metálico foi completada por quatro moléculas de água. Foi verificado que os retículos cristalinos destes sistemas são estabilizados por ligações de hidrogênio intra e intermoleculares. Os complexos da família cis-[M(L1)2(OH2)4 ainda foram estudados por voltametria cíclica onde foram observados picos de oxidação e redução referentes aos íons de FeII, CoII e NiII . A espectroscopia Mössbauer para o complexo cis-[Fe(L1)2(OH2)4] evidenciou o estado alto spin para o íon FeII no intervalo de temperatura de 4-300 K. As medidas magnéticas para os compostos cis-[Fe(L1)2(OH2)4] (M=CoII e FeII) mostraram um comportamento oriundo da anisotropia magnética axial e rômbica para estes sistemas, uma vez que as interações de troca são desprezíveis devido à grande distância entre os sítios metálicos no empacotamento cristalino. A resposta frente à inibição da enzima acetilcolinesterase dos complexos da família cis-[M(L1)2(OH2)4] revelou taxas de inibição entre 35 - 55% na concentração de 10 μmol L-1 . Utilizando a metodologia de difusão de vapor foram obtidos compostos de coordenação inéditos [Cu(L1)2(Py)2] e [Co(L1)2(Py)2]. Estes compostos também tiveram sua estrutura elucidada por difração de raios X por monocristal, sendo verificado que o complexo [Co(L1)2(Py)2] possui uma geometria tetraédrica distorcida onde o centro metálico e está coordenado a duas moléculas de piridina e dois átomos de grupos carboxilato de ligantes diferentes na forma monodentada. O complexo [Cu(L1)2(Py)2] possui um íon de CuII em uma geometria octaédrica distorcida, verificando-se a coordenação de dois ligantes L1 e duas moléculas de piridina.
publishDate 2019
dc.date.issued.fl_str_mv 2019-03-13
dc.date.accessioned.fl_str_mv 2023-12-22T03:03:25Z
dc.date.available.fl_str_mv 2023-12-22T03:03:25Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/masterThesis
format masterThesis
status_str publishedVersion
dc.identifier.citation.fl_str_mv DIAS, Isac Marinho. Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados. 2019. 170f. Dissertação (Mestrado em Química, Química Inorgânica). Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, RJ, 2019.
dc.identifier.uri.fl_str_mv https://rima.ufrrj.br/jspui/handle/20.500.14407/14604
identifier_str_mv DIAS, Isac Marinho. Síntese e caracterização de novos compostos de coordenação contendo ligantes pirazólicos funcionalizados. 2019. 170f. Dissertação (Mestrado em Química, Química Inorgânica). Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, RJ, 2019.
url https://rima.ufrrj.br/jspui/handle/20.500.14407/14604
dc.language.iso.fl_str_mv por
language por
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