Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro
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
Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Não Informado pela instituição
|
Departamento: |
Não Informado pela instituição
|
País: |
Não Informado pela instituição
|
Palavras-chave em Português: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/28257 |
Resumo: | Multi-nitrogenated ligands are versatile coordinating ligands to the transition metals. In this work, mono- and bis-triazenes, a tris-triazene, a tetrazenide and twelve metal complexes were synthesized, including the metal ions Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) and Cu(III). The triazenes and complexes were characterized by different analysis: infrared and UV-Vis spectroscopy, 1H, 13C and 31P NMR spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. The Cu(II) complex of the mono-triazenide N-oxide ligand [(2-Ph)ArNNN(®O)CH3]- (2) shows cis geometry on the coordinated center and possesses intramolecular Cu(II)···arene- interactions. Four complexes [(R’)ArNNNAr(R’’)Au(I)PPh3] were synthesized: 4 (R’ = OCH3, R’’ = 2-Ph), 6 (R’ = R’’ = 2-Ph), 8 (R’ = R’’ = 4-C(O)NH2) e 10 (R’ = 2-F, R’’ = 4-C(O)NH2). The crystal structure of 6 shows intramolecular Au(I)···arene- interaction. The complexes 8 and 10 are biologically active in vitro (antitumoral, antibacterial and DNA cleavage activities), showing better DNA cleavage in pH 6,5 at 50° C. These two complexes exhibit hydrogen bonding through the amide groups. The bis-triazenes [(R)ArNNN(H)(CH2)4N(H)NNAr(R)] 11 (R = H) and 15 (R = 2-C(O)NH2) are rotamers as showed in the 1H and 13C NMR spectra. The bis-triazene 11 shows interesting property in promoting the formation of binuclear complexes of Cu(II) (12), Ni(II) (13) and Pd(II) (14) with very short M−M distances and really strong M···M interactions. The Cu(II) complex (12) shows antiferromagnetism due to the strong Cu−Cu antiferromagnetic coupling. The three complexes (12, 13 and 14) exhibit intramolecular C−H···M anagostic interactions and intermolecular C−H···Ph interactions promoting supramolecular arrangement in the solid state. The copper tetrazenide complex 16 was synthesized from the reaction of the 2-amidephenylazide with Cu(OAc)2·H2O in EtOH in the presence of KOH and exemplifies a stable polimeric salt of potassium with the deprotonated amide group. A reaction mechanism of formation of the complex 16 is proposed. It is supposed , that the oxidation state of the Cu is +3, based on the square planar geometry of the copper, short Cu−N bond distances, different bond distances N−N in the tetrazenido chain (N−N=N−N), and diamagnetism. However, XANES and EXAFS should confirm it. The tripodal tris-triazene 17 is the first completely characterized of this class of molecule including the X-ray diffraction on single crystal analysis. Depending on the crystallization conditions, the crystal structures of 17 show a water or a DMSO molecule inside the cavity formed by the three triazene chains, depending on the crystallization conditions. The tristriazenide gives a trinuclear complex of Cu(II) (18) with two ligands double deprotonated. This complex is paramagnetic. The complexes 19 (M = Cu(I)) and 20 (M = Ag(I)) have similar structure to each other, being salts where the anionic part is composed by two ligands tris-triazenides completely deprotonated surrounding a cluster of the M5 type, while the cationic part is composed by the M+(PPh3)3OH2 fragment. |
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Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitroMono-, bis- and tris-triazenes, tetrazene and complexes of Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) AND Cu(III): synthesis, characterization, crystal structure, in vitro antitumoral, antibacterial and DNA cleavege activitiesMono-triazenoBis-triazenoTris-triazeno tripodalTriazeno N-óxidoTetrazenoComplexosCu(I)Ag(I)Au(I)Cu(II)Ni(II)Pd(II)Cu(III)Susceptibilidade magnéticaEstrutura cristalinaAtividades antitumoralAntibacteriana e de clivagem do DNA in vitroQuímica supramolecularMono-triazeneBis-triazeneTripodal tris-triazeneTriazene N-oxideTetrazenideComplexesMagnetic susceptibilityCrystal structureIn vitro antitumoralAntibacterial and DNA cleavage activitiesSupramolecular chemistryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAMulti-nitrogenated ligands are versatile coordinating ligands to the transition metals. In this work, mono- and bis-triazenes, a tris-triazene, a tetrazenide and twelve metal complexes were synthesized, including the metal ions Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) and Cu(III). The triazenes and complexes were characterized by different analysis: infrared and UV-Vis spectroscopy, 1H, 13C and 31P NMR spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. The Cu(II) complex of the mono-triazenide N-oxide ligand [(2-Ph)ArNNN(®O)CH3]- (2) shows cis geometry on the coordinated center and possesses intramolecular Cu(II)···arene- interactions. Four complexes [(R’)ArNNNAr(R’’)Au(I)PPh3] were synthesized: 4 (R’ = OCH3, R’’ = 2-Ph), 6 (R’ = R’’ = 2-Ph), 8 (R’ = R’’ = 4-C(O)NH2) e 10 (R’ = 2-F, R’’ = 4-C(O)NH2). The crystal structure of 6 shows intramolecular Au(I)···arene- interaction. The complexes 8 and 10 are biologically active in vitro (antitumoral, antibacterial and DNA cleavage activities), showing better DNA cleavage in pH 6,5 at 50° C. These two complexes exhibit hydrogen bonding through the amide groups. The bis-triazenes [(R)ArNNN(H)(CH2)4N(H)NNAr(R)] 11 (R = H) and 15 (R = 2-C(O)NH2) are rotamers as showed in the 1H and 13C NMR spectra. The bis-triazene 11 shows interesting property in promoting the formation of binuclear complexes of Cu(II) (12), Ni(II) (13) and Pd(II) (14) with very short M−M distances and really strong M···M interactions. The Cu(II) complex (12) shows antiferromagnetism due to the strong Cu−Cu antiferromagnetic coupling. The three complexes (12, 13 and 14) exhibit intramolecular C−H···M anagostic interactions and intermolecular C−H···Ph interactions promoting supramolecular arrangement in the solid state. The copper tetrazenide complex 16 was synthesized from the reaction of the 2-amidephenylazide with Cu(OAc)2·H2O in EtOH in the presence of KOH and exemplifies a stable polimeric salt of potassium with the deprotonated amide group. A reaction mechanism of formation of the complex 16 is proposed. It is supposed , that the oxidation state of the Cu is +3, based on the square planar geometry of the copper, short Cu−N bond distances, different bond distances N−N in the tetrazenido chain (N−N=N−N), and diamagnetism. However, XANES and EXAFS should confirm it. The tripodal tris-triazene 17 is the first completely characterized of this class of molecule including the X-ray diffraction on single crystal analysis. Depending on the crystallization conditions, the crystal structures of 17 show a water or a DMSO molecule inside the cavity formed by the three triazene chains, depending on the crystallization conditions. The tristriazenide gives a trinuclear complex of Cu(II) (18) with two ligands double deprotonated. This complex is paramagnetic. The complexes 19 (M = Cu(I)) and 20 (M = Ag(I)) have similar structure to each other, being salts where the anionic part is composed by two ligands tris-triazenides completely deprotonated surrounding a cluster of the M5 type, while the cationic part is composed by the M+(PPh3)3OH2 fragment.Ligantes multi-nitrogenados possuem versatilidade para coordenação a metais de transição. Neste trabalho, foram sintetizados mono- e bis-triazenos, um tris-triazeno, um tetrazenido e doze complexos metálicos com os íons metálicos Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) e Cu(III). Os triazenos e complexos foram caracterizados por espectroscopia de IV e UV-Vis, espectroscopia de RMN 1H, 13C e 31P, espectrometria de massas de baixa ou alta resolução (EI, ESI, ESI(+)-TOF e ESI(- )-TOF) e difração de raios X em monocristal. O complexo de Cu(II) com o ligante mono-triazenido Nóxido [(2-Ph)ArNNN(®O)CH3]- (2) apresenta-se com geometria cis no centro de coordenação e possui interação Cu(II)···areno- intramolecular. Quatro complexos [(R’)ArNNNAr(R’’)Au(I)PPh3] foram sintetizados: 4 (R’ = OCH3, R’’ = 2-Ph), 6 (R’ = R’’ = 2-Ph), 8 (R’ = R’’ = 4-C(O)NH2) e 10 (R’ = 2-F, R’’ = 4-C(O)NH2). A estrutura cristalina do complexo 6 mostra interação do tipo Au(I)···areno- intramolecular. Os complexos 8 e 10 são biologicamente ativos in vitro (atividades antitumoral, antibacteriana e de clivagem do DNA), mostrando melhor atividade de clivagem do DNA em pH 6,5 a 50° C. Estes dois complexos apresentam grande número de ligações de hidrogênio através dos grupos amida. Os bis-triazenos [(R)ArNNN(H)(CH2)4N(H)NNAr(R)] 11 (R = H) e 15 (R = 2- C(O)NH2) apresentam-se na forma de isômeros de rotação como mostra a espectroscopia de RMN 1H e 13C. O bis-triazeno 11 possui interessante propriedade de formar complexos binucleares de Cu(II) (12), Ni(II) (13) e Pd(II) (14) com curtas distâncias M−M e interações M···M. O complexo de Cu(II) (12) possui antiferromagnetismo devido ao forte acoplamento antiferromagnético Cu−Cu. Os três complexos (12, 13 e 14) formam interações anagósticas intramoleculares do tipo C−H···M e interações intermoleculares do tipo C−H···Ph. O complexo tetrazenido de cobre (16) foi sintetizado a partir da reação da 2-amidofenilazida com Cu(OAc)2·H2O em EtOH na presenta de KOH e apresenta-se na forma de um sal polimérico estável de potássio como o grupo amida desprotonado. Um mecanismo de formação do complexo 16 é proposto. Através da geometria de coordenação quadrática do cobre, das curtas distâncias de ligações Cu−N, das distâncias de ligação na cadeia tetrazenido, da susceptibilidade magnética, pode-se supor que o estado de oxidação do Cu é +3. Contudo, análises de XANES e EXAFS deveriam confirmar isto. O tris-triazeno (N(2-PhN(H)NNPh)3) 17 tripodal é o primeiro completamente caracterizado, incluindo a estrutura cristalina determinada por difração de raios X e inclui uma molécula de água ou de DMSO na cavidade formada pelas três cadeias triazeno, dependendo das condições de cristalização. O tris-triazenido forma o complexo de Cu(II) trinuclear (18) com dois ligantes duplamente desprotonados. Este complexo é paramagnético. Os complexos 19 (M = Cu(I)) e 20 (M = Ag(I)) possuem estruturas similares entre si, sendo sais nos quais a parte aniônica é composta por dois ligantes tris-triazenidos completamente desprotonados envolvendo um cluster do tipo M5 e, a parte catiônica possui o fragmento [M(PPh3)3(OH2)]+.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasHorner, Manfredohttp://lattes.cnpq.br/8922528250830998Beck, JohannesNunes, Fábio SouzaSantos, Aline Joana Rolina Wohlmuth Alves dosBack, Davi FernandoFenner, HertonParaginski, Gustavo Luiz2023-03-17T13:12:42Z2023-03-17T13:12:42Z2013-01-31info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/28257porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2023-03-17T13:12:42Zoai:repositorio.ufsm.br:1/28257Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-03-17T13:12:42Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro Mono-, bis- and tris-triazenes, tetrazene and complexes of Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) AND Cu(III): synthesis, characterization, crystal structure, in vitro antitumoral, antibacterial and DNA cleavege activities |
title |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
spellingShingle |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro Paraginski, Gustavo Luiz Mono-triazeno Bis-triazeno Tris-triazeno tripodal Triazeno N-óxido Tetrazeno Complexos Cu(I) Ag(I) Au(I) Cu(II) Ni(II) Pd(II) Cu(III) Susceptibilidade magnética Estrutura cristalina Atividades antitumoral Antibacteriana e de clivagem do DNA in vitro Química supramolecular Mono-triazene Bis-triazene Tripodal tris-triazene Triazene N-oxide Tetrazenide Complexes Magnetic susceptibility Crystal structure In vitro antitumoral Antibacterial and DNA cleavage activities Supramolecular chemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
title_full |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
title_fullStr |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
title_full_unstemmed |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
title_sort |
Mono-, bis- e tris-triazenos, tetrazeno e complexos de Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) E Cu(III): síntese, caracterização, estrutura cristalina, atividades antitumoral, antibacteriana e de clivagem do DNA in vitro |
author |
Paraginski, Gustavo Luiz |
author_facet |
Paraginski, Gustavo Luiz |
author_role |
author |
dc.contributor.none.fl_str_mv |
Horner, Manfredo http://lattes.cnpq.br/8922528250830998 Beck, Johannes Nunes, Fábio Souza Santos, Aline Joana Rolina Wohlmuth Alves dos Back, Davi Fernando Fenner, Herton |
dc.contributor.author.fl_str_mv |
Paraginski, Gustavo Luiz |
dc.subject.por.fl_str_mv |
Mono-triazeno Bis-triazeno Tris-triazeno tripodal Triazeno N-óxido Tetrazeno Complexos Cu(I) Ag(I) Au(I) Cu(II) Ni(II) Pd(II) Cu(III) Susceptibilidade magnética Estrutura cristalina Atividades antitumoral Antibacteriana e de clivagem do DNA in vitro Química supramolecular Mono-triazene Bis-triazene Tripodal tris-triazene Triazene N-oxide Tetrazenide Complexes Magnetic susceptibility Crystal structure In vitro antitumoral Antibacterial and DNA cleavage activities Supramolecular chemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Mono-triazeno Bis-triazeno Tris-triazeno tripodal Triazeno N-óxido Tetrazeno Complexos Cu(I) Ag(I) Au(I) Cu(II) Ni(II) Pd(II) Cu(III) Susceptibilidade magnética Estrutura cristalina Atividades antitumoral Antibacteriana e de clivagem do DNA in vitro Química supramolecular Mono-triazene Bis-triazene Tripodal tris-triazene Triazene N-oxide Tetrazenide Complexes Magnetic susceptibility Crystal structure In vitro antitumoral Antibacterial and DNA cleavage activities Supramolecular chemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Multi-nitrogenated ligands are versatile coordinating ligands to the transition metals. In this work, mono- and bis-triazenes, a tris-triazene, a tetrazenide and twelve metal complexes were synthesized, including the metal ions Cu(I), Ag(I), Au(I), Cu(II), Ni(II), Pd(II) and Cu(III). The triazenes and complexes were characterized by different analysis: infrared and UV-Vis spectroscopy, 1H, 13C and 31P NMR spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. The Cu(II) complex of the mono-triazenide N-oxide ligand [(2-Ph)ArNNN(®O)CH3]- (2) shows cis geometry on the coordinated center and possesses intramolecular Cu(II)···arene- interactions. Four complexes [(R’)ArNNNAr(R’’)Au(I)PPh3] were synthesized: 4 (R’ = OCH3, R’’ = 2-Ph), 6 (R’ = R’’ = 2-Ph), 8 (R’ = R’’ = 4-C(O)NH2) e 10 (R’ = 2-F, R’’ = 4-C(O)NH2). The crystal structure of 6 shows intramolecular Au(I)···arene- interaction. The complexes 8 and 10 are biologically active in vitro (antitumoral, antibacterial and DNA cleavage activities), showing better DNA cleavage in pH 6,5 at 50° C. These two complexes exhibit hydrogen bonding through the amide groups. The bis-triazenes [(R)ArNNN(H)(CH2)4N(H)NNAr(R)] 11 (R = H) and 15 (R = 2-C(O)NH2) are rotamers as showed in the 1H and 13C NMR spectra. The bis-triazene 11 shows interesting property in promoting the formation of binuclear complexes of Cu(II) (12), Ni(II) (13) and Pd(II) (14) with very short M−M distances and really strong M···M interactions. The Cu(II) complex (12) shows antiferromagnetism due to the strong Cu−Cu antiferromagnetic coupling. The three complexes (12, 13 and 14) exhibit intramolecular C−H···M anagostic interactions and intermolecular C−H···Ph interactions promoting supramolecular arrangement in the solid state. The copper tetrazenide complex 16 was synthesized from the reaction of the 2-amidephenylazide with Cu(OAc)2·H2O in EtOH in the presence of KOH and exemplifies a stable polimeric salt of potassium with the deprotonated amide group. A reaction mechanism of formation of the complex 16 is proposed. It is supposed , that the oxidation state of the Cu is +3, based on the square planar geometry of the copper, short Cu−N bond distances, different bond distances N−N in the tetrazenido chain (N−N=N−N), and diamagnetism. However, XANES and EXAFS should confirm it. The tripodal tris-triazene 17 is the first completely characterized of this class of molecule including the X-ray diffraction on single crystal analysis. Depending on the crystallization conditions, the crystal structures of 17 show a water or a DMSO molecule inside the cavity formed by the three triazene chains, depending on the crystallization conditions. The tristriazenide gives a trinuclear complex of Cu(II) (18) with two ligands double deprotonated. This complex is paramagnetic. The complexes 19 (M = Cu(I)) and 20 (M = Ag(I)) have similar structure to each other, being salts where the anionic part is composed by two ligands tris-triazenides completely deprotonated surrounding a cluster of the M5 type, while the cationic part is composed by the M+(PPh3)3OH2 fragment. |
publishDate |
2013 |
dc.date.none.fl_str_mv |
2013-01-31 2023-03-17T13:12:42Z 2023-03-17T13:12:42Z |
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/1/28257 |
url |
http://repositorio.ufsm.br/handle/1/28257 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805930118359547904 |