Dissertations / Theses on the topic 'Pd(II) chemistry'
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Moni, Lucky. "Ni(II) and Pd(II) based catalysts for α-olefin polymerisation." Master's thesis, University of Cape Town, 1999. http://hdl.handle.net/11427/9955.
Full textNdlovu, Mazwi Eugene. "Development of Pd(II)- and Pt(II)-based catalysts for polymerisation and oligomerisation of [alpha]-olefins." Master's thesis, University of Cape Town, 2001. http://hdl.handle.net/11427/6351.
Full textIncludes bibliographical references.
The polymers were investigated by DSC and TGA to determine their melting point endotherms and thermal stability. All polymers exhibited low thermal stabilities and low melting point endotherms.
Bruce, Jocelyn. "Potentially fluorescent ligands based on the N,N-dialkyl -N'- aroylthiourea motif and their Pt(II) and Pd(II) complexes /." Thesis, Link to the online version, 2005. http://hdl.handle.net/10019/986.
Full textMiller, Jörn Derrick Schuster. "Synthesis of N-alkyl-and N,N-dialkyl-N'-acyl- and N'-aroythioureas, and aspects of their co-ordination chemistry with Pt(II)and Pd(II)." Doctoral thesis, University of Cape Town, 2000. http://hdl.handle.net/11427/6336.
Full textThe synthesis of simple, and also bipodal N-substituted N'-acyl- and N'-aroylthiourea ligands has been investigated, along with aspects of their co-ordination chemistry to Pt(II) and Pd(II). The ligands are commonly produced by reacting a secondary or primary amine with an acyl or aroyl isothiocyanate. This synthesis requires nucleophilic addition of the amine to the thiocarbonyl carbon of the acyl or aroyl isothocyanate. However, a competitive side-reaction frequently occurs because the amine nucleophile can attack the carbonyl carbon of the isothiocyanate reagent instead. This leads to substitution of the isothiocyanate moiety and the formation of an N-substituted amide.
Lim, Ngiap Kie 1972. "Coupling of insertion and ring-opening polymerizations on a Pd(II) Center : a potential route to novel block co-polymers." Thesis, McGill University, 1999. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=29908.
Full textThe feasibility of combining this ring-opening reaction to insertion polymerization to generate new block co-polymers is subsequently investigated, and it forms the primary objective of the study.
The dual-functional palladium(II) complex (bipy)Pd(CH3)(NCCH 3)+OTf- is found to mediate a novel, single-step coupling of insertion and ring-opened monomers (CO, norbornene, THF) into new polymers. This coupling process follows an unusual route, involving enol lactone as an intermediate, and facilitated by weak Lewis acid. Similar coupling chemistry has been applied to the synthesis of polyTHF end-capped with a small polynorbornene fragment.
Moro, Antonio Carlos [UNESP]. "Espécies moleculares e supramoleculares de 'PD'(II)' com ligantes mono, bi e polidentados : caracterização estrutural e atividades biológicas." Universidade Estadual Paulista (UNESP), 2011. http://hdl.handle.net/11449/105783.
Full textConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Os ciclopaladados do tipo [Pd(dmba)(X)L] e [Pd2(dmba)2(μ-L)] (Hdmba = N,N-dimetilbenzilamina; X = haletos ou pseudo-haletos; L = ligantes mono ou bidentados) são compostos estáveis ao ar e empregados em vários estudos biológicos devido a seus potenciais antitumorais. Este trabalho contempla a síntese e caracterização estrutural dos ciclopaladados mononucleares [Pd(dmba)(X)tu] (tu = tiouréia; X = Br (8), I (9)), binucleares [Pd2(dmba)2(X)2(μ-bpp)] (bpp = 1,3-bis(4-piridil)propano; X = Cl (10), Br (11), NCO (12), N3 (13)), e poliméricos [{Pd(dmba)}2{μ-Fe(CN)5NO}]n (14), [{Pd(dmba)}2{μ-Pd(CN)4}]n (15), bem como das espécies [Pd2(Cl)4(PPh3)2(μ-ted)] (16), [Pd2(Br)2(Cl)2(PPh3)2(μ-ted)] (17) e [Pd2(N3)4(PPh3)2(μ-ted)] (18) (PPh3 = trifenilfosfina; ted = trietilenodiamina). As estruturas foram propostas com base em medidas de análise elementar, espectroscopia vibracional na região do infravermelho e espectroscopia de ressonância magnética nuclear. As estruturas de [Pd(dmba)(μ-Br)]2 (4), [Pd(dmba)(Br)tu] (8) e [Pd2(N3)4(PPh3)2(μ-ted)] (18) foram determinadas via difração de raios X por monocristal. Este estudo evidenciou também que as ligações hidrogênio são importantes para direcionar a auto-associação das espécies 8 e 18 durante a cristalização. O comportamento térmico dos compostos 10-12, 14-17 foi investigado por termogravimetria e análise térmica diferencial e os resíduos caracterizados por difração de raios X, método do pó. Além destes, foram sintetizadas as espécies conhecidas [Pd(dmba)(Cl)tu] (6) e [Pd(dmba)(N3)tu] (7), com o intuito de investigar suas atividades biológicas e compará-las com as de outras espécies que apresentam os mesmos ligantes (dmba e tu). As citotoxicidades in vitro dos ciclopaladados e da cisplatina...
Cyclopalladated complexes of the type [Pd(dmba)(X)L] and [Pd2(dmba)2(μ-L)] (Hdmba = N,N-dimethylbenzylamine; X = halides or pseudohalides; L = monodentate or bidentate ligands) are air stable compounds and nowadays employed in several biological studies because of their potential antitumour activities. This research deals with the synthesis and structural characterization of the mononuclear cyclopalladated compounds [Pd(dmba)(X)tu] (tu = thiourea; X = Br (8), I (9)), dinuclear [Pd2(dmba)2(X)2(μ-bpp)] (bpp = 1,3-bis(4-pyridyl)propane); X = Cl (10), Br (11), NCO (12), N3 (13)), and polymers [{Pd(dmba)}2{μ-Fe(CN)5NO}]n (14), [{Pd(dmba)}2{μ-Pd(CN)4}]n (15), as well of the species [Pd2(Cl)4(PPh3)2(μ-ted)] (16), [Pd2(Br)2(Cl)2(PPh3)2(μ-ted)] (17) and [Pd2(N3)4(PPh3)2(μ-ted)] (18) (PPh3 = triphenylphosphine; ted = triethylenediamine). The compounds structures were proposed on the basis of elemental analysis, infrared vibrational spectroscopy and nuclear magnetic resonance spectroscopy. The crystal and molecular structures of [Pd(dmba)(μ-Br)]2 (4), [Pd(dmba)(Br)tu] (8) and [Pd2(N3)4(PPh3)2(μ-ted)] (18) were determined by single-crystal X-ray diffraction measurements. This study also showed that the hydrogen bonds play an important role for directing self-assembly of 8 and 18 species during the crystallization. The thermal behavior of the compounds 10-12, 14-17 was studied by thermogravimetry and differential thermal analysis and the final decomposition products were identified by X-ray powder diffraction. In addition to these compounds, the known ones [Pd(dmba)(Cl)tu] (6) and [Pd(dmba)(N3)tu] (7) were prepared in order to have their biological activities studied and compared with other ones containing the same ligands (dmba and tu). In vitro cytotoxicity assays of cyclopalladated complexes and cisplatin (standard antitumour drug) were carried... (Complete abstract click electronic access below)
Moro, Antonio Carlos. "Espécies moleculares e supramoleculares de 'PD'(II)' com ligantes mono, bi e polidentados : caracterização estrutural e atividades biológicas /." Araraquara [s.n.], 2011. http://hdl.handle.net/11449/105783.
Full textCoorientador: Adelino Vieira de Godoy Netto
Banca: Gilbert Bannach
Banca: Douglas Wagner Franco
Banca: Roberto Santana da Silva
Banca: Victor Marcelo Deflon
Resumo: Os ciclopaladados do tipo [Pd(dmba)(X)L] e [Pd2(dmba)2(μ-L)] (Hdmba = N,N-dimetilbenzilamina; X = haletos ou pseudo-haletos; L = ligantes mono ou bidentados) são compostos estáveis ao ar e empregados em vários estudos biológicos devido a seus potenciais antitumorais. Este trabalho contempla a síntese e caracterização estrutural dos ciclopaladados mononucleares [Pd(dmba)(X)tu] (tu = tiouréia; X = Br (8), I (9)), binucleares [Pd2(dmba)2(X)2(μ-bpp)] (bpp = 1,3-bis(4-piridil)propano; X = Cl (10), Br (11), NCO (12), N3 (13)), e poliméricos [{Pd(dmba)}2{μ-Fe(CN)5NO}]n (14), [{Pd(dmba)}2{μ-Pd(CN)4}]n (15), bem como das espécies [Pd2(Cl)4(PPh3)2(μ-ted)] (16), [Pd2(Br)2(Cl)2(PPh3)2(μ-ted)] (17) e [Pd2(N3)4(PPh3)2(μ-ted)] (18) (PPh3 = trifenilfosfina; ted = trietilenodiamina). As estruturas foram propostas com base em medidas de análise elementar, espectroscopia vibracional na região do infravermelho e espectroscopia de ressonância magnética nuclear. As estruturas de [Pd(dmba)(μ-Br)]2 (4), [Pd(dmba)(Br)tu] (8) e [Pd2(N3)4(PPh3)2(μ-ted)] (18) foram determinadas via difração de raios X por monocristal. Este estudo evidenciou também que as ligações hidrogênio são importantes para direcionar a auto-associação das espécies 8 e 18 durante a cristalização. O comportamento térmico dos compostos 10-12, 14-17 foi investigado por termogravimetria e análise térmica diferencial e os resíduos caracterizados por difração de raios X, método do pó. Além destes, foram sintetizadas as espécies conhecidas [Pd(dmba)(Cl)tu] (6) e [Pd(dmba)(N3)tu] (7), com o intuito de investigar suas atividades biológicas e compará-las com as de outras espécies que apresentam os mesmos ligantes (dmba e tu). As citotoxicidades in vitro dos ciclopaladados e da cisplatina... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Cyclopalladated complexes of the type [Pd(dmba)(X)L] and [Pd2(dmba)2(μ-L)] (Hdmba = N,N-dimethylbenzylamine; X = halides or pseudohalides; L = monodentate or bidentate ligands) are air stable compounds and nowadays employed in several biological studies because of their potential antitumour activities. This research deals with the synthesis and structural characterization of the mononuclear cyclopalladated compounds [Pd(dmba)(X)tu] (tu = thiourea; X = Br (8), I (9)), dinuclear [Pd2(dmba)2(X)2(μ-bpp)] (bpp = 1,3-bis(4-pyridyl)propane); X = Cl (10), Br (11), NCO (12), N3 (13)), and polymers [{Pd(dmba)}2{μ-Fe(CN)5NO}]n (14), [{Pd(dmba)}2{μ-Pd(CN)4}]n (15), as well of the species [Pd2(Cl)4(PPh3)2(μ-ted)] (16), [Pd2(Br)2(Cl)2(PPh3)2(μ-ted)] (17) and [Pd2(N3)4(PPh3)2(μ-ted)] (18) (PPh3 = triphenylphosphine; ted = triethylenediamine). The compounds structures were proposed on the basis of elemental analysis, infrared vibrational spectroscopy and nuclear magnetic resonance spectroscopy. The crystal and molecular structures of [Pd(dmba)(μ-Br)]2 (4), [Pd(dmba)(Br)tu] (8) and [Pd2(N3)4(PPh3)2(μ-ted)] (18) were determined by single-crystal X-ray diffraction measurements. This study also showed that the hydrogen bonds play an important role for directing self-assembly of 8 and 18 species during the crystallization. The thermal behavior of the compounds 10-12, 14-17 was studied by thermogravimetry and differential thermal analysis and the final decomposition products were identified by X-ray powder diffraction. In addition to these compounds, the known ones [Pd(dmba)(Cl)tu] (6) and [Pd(dmba)(N3)tu] (7) were prepared in order to have their biological activities studied and compared with other ones containing the same ligands (dmba and tu). In vitro cytotoxicity assays of cyclopalladated complexes and cisplatin (standard antitumour drug) were carried... (Complete abstract click electronic access below)
Doutor
Moro, Antonio Carlos [UNESP]. "Espécies moleculares e supramoleculares de Pd(II) contendo ligantes N,S doadores: síntese e caracterização." Universidade Estadual Paulista (UNESP), 2007. http://hdl.handle.net/11449/97949.
Full textCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Este trabalho contempla a preparação de novas espécies de paládio (II), ciclometaladas ou não, a partir dos precursores [Pd(dmba)(æ-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) e [PdCl2(CH3CN)2]. Os complexos [Pd(dmba)(X)(tu)] (tu = tiouréia; X = Cl, N3, NCO) foram obtidos via clivagem dos ciclopaladados diméricos [Pd(dmba)(æ-X)]2 pelo ligante tiouréia, bem como os compostos [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS = 2-quinolinatiolato; L = 8-qnS = 8-quinolinatiolato) mediante substituição parcial do cianato em ponte pelos ligantes 2-qnS e 8-qnS, respectivamente. Os dados oriundos da investigação espectroscópica dos mesmos segundo as técnicas de espectroscopia vibracional na região do IV, RMN de 1H e 13C permitiram diagnosticar o modo de coordenação dos ligantes dmba, tiouréia, 2-quinolinatiolato, 8-quinolinatiolato e pseudo-haletos ao paládio. Tais dados, juntamente com outros da literatura e analíticos, confirmaram os monômeros [Pd(dmba)(X)(tu)] (X = Cl, N3, NCO) e os compostos binucleares [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS). Realizou-se, também, a investigação do comportamento térmico dos ciclopaladados [Pd(dmba)(X)(tu)] (X = Cl, NCO) e [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS), via obtenção das curvas TG/DTA. A análise térmica permitiu o estabelecimento da ordem de estabilidade, bem como confirmou a estequiometria dos compostos. Outros complexos de Pd (II) investigados, neste trabalho, foram [Pd(X)2(tu)(PPh3)] (X = Cl, N3, CN, NCS) obtidos via reação entre os ligantes tiouréia e trifenilfosfina (PPh3) e o composto [PdCl2(CH3CN)2]. Obteve-se também a espécie [Pd(8- qnS)2] da reação entre o cloro composto [PdCl2(CH3CN)2] e o tioligante 8-qnS. Os dados provenientes da investigação destes compostos mediante a espectroscopia vibracional na região do IV permitiram diagnosticar a coordenação dos ligantes ao centro metálico.
This main goal of this work was to synthesize new compounds from the [Pd(dmba)(æ- X)]2 (dmba = N,N-dimethylbenzylamine; X = Cl, N3, NCO) e [PdCl2(CH3CN)2] precursors. The reactions between [Pd(dmba)(æ-X)]2 (X = Cl, N3, NCO) and tiourea (tu), occurred by cleavage of the dimerics cyclopalladated, leading to the compounds [Pd(dmba)(X)(tu)]. The dinuclear species [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS) were obtained by reactions between [Pd(dmba)(æ-NCO)]2 precursor and 2-qnS and 8-qnS ligands. From IR data, it was evidenced the terminal coordination of the N3 and NCO groups in [Pd(dmba)(X)(tu)] complexes, whereas in the complexes of the type [Pd2(dmba)2(æ-NCO)(æ-L)] the NCO, 2-qnS and 8-qnS ligands were found in theirs bridging forms. The results obtained from 1H, 13C NMR signals showed significant shifts related to the free ligands, indicating their coordination to Pd. The thermoanalytical data, from TG and DTA curves, for the [Pd(dmba)(X)(tu)] (X = Cl, NCO) and [Pd2(dmba)2(æ-NCO)(æ-L)] species are described. The main objectives of the thermal analysis of these compounds is to enlight the influence of the thioligands (tu, 2-qnS and 8-qnS) in the initial decomposition temperature, as well as to propose decomposition steps. Mononuclear species of general formulae [Pd(X)2(tu)(PPh3)] (X = Cl, N3, CN, NCS) were also synthesized by reacting [PdCl2(CH3CN)2] precursor with ligands (tu, PPh3 and pseudohalides). From IR data, it was evidenced the S-monodentate coordination of the tiourea molecule in [Pd(X)2(tu)(PPh3)]. The solution behavior of complexes [Pd(X)2(tu)(PPh3)] (X = Cl, NCS) was investigated by 1H, 13C and 31P NMR spectra. The crystal and molecular structure of cis-[PdCl2(t u)(PPh3].CH3OH were determined by X-ray diffraction of monocrystals. This study showed that the N-HCl-Pd and C-HCl-Pd hydrogen bonds play an important role in the self-assembly this cis-palladium complex as building blocks.
Moro, Antonio Carlos. "Espécies moleculares e supramoleculares de Pd(II) contendo ligantes N,S doadores : síntese e caracterização /." Araraquara : [s.n.], 2007. http://hdl.handle.net/11449/97949.
Full textBanca: Sandra Helena Pulcinelli
Banca: Alzir Azevedo Batista
Resumo: Este trabalho contempla a preparação de novas espécies de paládio (II), ciclometaladas ou não, a partir dos precursores [Pd(dmba)(æ-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) e [PdCl2(CH3CN)2]. Os complexos [Pd(dmba)(X)(tu)] (tu = tiouréia; X = Cl, N3, NCO) foram obtidos via clivagem dos ciclopaladados diméricos [Pd(dmba)(æ-X)]2 pelo ligante tiouréia, bem como os compostos [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS = 2-quinolinatiolato; L = 8-qnS = 8-quinolinatiolato) mediante substituição parcial do cianato em ponte pelos ligantes 2-qnS e 8-qnS, respectivamente. Os dados oriundos da investigação espectroscópica dos mesmos segundo as técnicas de espectroscopia vibracional na região do IV, RMN de 1H e 13C permitiram diagnosticar o modo de coordenação dos ligantes dmba, tiouréia, 2-quinolinatiolato, 8-quinolinatiolato e pseudo-haletos ao paládio. Tais dados, juntamente com outros da literatura e analíticos, confirmaram os monômeros [Pd(dmba)(X)(tu)] (X = Cl, N3, NCO) e os compostos binucleares [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS). Realizou-se, também, a investigação do comportamento térmico dos ciclopaladados [Pd(dmba)(X)(tu)] (X = Cl, NCO) e [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS), via obtenção das curvas TG/DTA. A análise térmica permitiu o estabelecimento da ordem de estabilidade, bem como confirmou a estequiometria dos compostos. Outros complexos de Pd (II) investigados, neste trabalho, foram [Pd(X)2(tu)(PPh3)] (X = Cl, N3, CN, NCS) obtidos via reação entre os ligantes tiouréia e trifenilfosfina (PPh3) e o composto [PdCl2(CH3CN)2]. Obteve-se também a espécie [Pd(8- qnS)2] da reação entre o cloro composto [PdCl2(CH3CN)2] e o tioligante 8-qnS. Os dados provenientes da investigação destes compostos mediante a espectroscopia vibracional na região do IV permitiram diagnosticar a coordenação dos ligantes ao centro metálico.
Abstract: This main goal of this work was to synthesize new compounds from the [Pd(dmba)(æ- X)]2 (dmba = N,N-dimethylbenzylamine; X = Cl, N3, NCO) e [PdCl2(CH3CN)2] precursors. The reactions between [Pd(dmba)(æ-X)]2 (X = Cl, N3, NCO) and tiourea (tu), occurred by cleavage of the dimerics cyclopalladated, leading to the compounds [Pd(dmba)(X)(tu)]. The dinuclear species [Pd2(dmba)2(æ-NCO)(æ-L)] (L = 2-qnS, 8-qnS) were obtained by reactions between [Pd(dmba)(æ-NCO)]2 precursor and 2-qnS and 8-qnS ligands. From IR data, it was evidenced the terminal coordination of the N3 and NCO groups in [Pd(dmba)(X)(tu)] complexes, whereas in the complexes of the type [Pd2(dmba)2(æ-NCO)(æ-L)] the NCO, 2-qnS and 8-qnS ligands were found in theirs bridging forms. The results obtained from 1H, 13C NMR signals showed significant shifts related to the free ligands, indicating their coordination to Pd. The thermoanalytical data, from TG and DTA curves, for the [Pd(dmba)(X)(tu)] (X = Cl, NCO) and [Pd2(dmba)2(æ-NCO)(æ-L)] species are described. The main objectives of the thermal analysis of these compounds is to enlight the influence of the thioligands (tu, 2-qnS and 8-qnS) in the initial decomposition temperature, as well as to propose decomposition steps. Mononuclear species of general formulae [Pd(X)2(tu)(PPh3)] (X = Cl, N3, CN, NCS) were also synthesized by reacting [PdCl2(CH3CN)2] precursor with ligands (tu, PPh3 and pseudohalides). From IR data, it was evidenced the S-monodentate coordination of the tiourea molecule in [Pd(X)2(tu)(PPh3)]. The solution behavior of complexes [Pd(X)2(tu)(PPh3)] (X = Cl, NCS) was investigated by 1H, 13C and 31P NMR spectra. The crystal and molecular structure of cis-[PdCl2(t u)(PPh3].CH3OH were determined by X-ray diffraction of monocrystals. This study showed that the N-HCl-Pd and C-HCl-Pd hydrogen bonds play an important role in the self-assembly this cis-palladium complex as building blocks.
Mestre
Barra, Carolina Valério [UNESP]. "Investigação das potencialidades de complexos pirazólicos de Pd (II) no desenvolvimento de novas metalo-drogas." Universidade Estadual Paulista (UNESP), 2010. http://hdl.handle.net/11449/97916.
Full textConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
A quimioterapia é uma das principais formas de combate ao câncer. Sendo assim, muitas pesquisas vêm sendo feitas com o objetivo de desenvolver compostos que solucionem, ou minimizem, os problemas decorrentes deste tipo de tratamento, como os efeitos colaterais e a resistência que as células desenvolvem aos medicamentos. Os pirazóis e seus complexos são conhecidos por possuírem atividade antitumoral, antiinflamatória, antibacteriana e antipirética. Tendo em vista estas propriedades, ligantes pirazólicos foram utilizados na síntese de complexos de paládio(II) com a finalidade de obter compostos com atividade antitumoral. A escolha deste metal foi baseada na similaridade entre sua química de coordenação e a da platina(II), cujos complexos, como a cisplatina e a carboplatina, são amplamente utilizados como agentes antitumorais. Neste contexto, o presente trabalho descreve a síntese, caracterização e avaliação da atividade antitumoral de duas séries de compostos paládio(II) de fórmula geral [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimetil-4-iodopirazol; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-metilpirazol; X = Cl (5), Br (6), I (7), SCN (8)}. Os compostos foram caracterizados por análise elementar, espectroscopia vibracional na região do infravermelho, ressonância magnética nuclear de 1 H e 13 C{ 1 H}, termogravimetria e análise térmica diferencial. Os complexos sintetizados e os ligantes livres foram submetidos a testes de atividade citotóxica frente a células tumorais murinas. A cisplatina foi usada como droga padrão, sendo submetida às mesmas condições. A citotoxicidade dos compostos 1-4 também foi avaliada frente a macrófagos peritoneais de camundongos
Chemotherapy is one of the main methods of treating cancer. Thus, much research has been undertaken with the aim of developing compounds that can solve or minimize the problems caused by this type of treatment, as the side effects and cell resistance. Pyrazoles and their complexes are known to possess antitumor, anti-inflammatory, antiamoebic, antibacterial, antipyretic activities. Considering these properties, pyrazole ligands were used in the synthesis of palladium(II) complexes with the aim to obtain compounds displaying antitumor activity. The choice for using this metal was based on the similarity of its coordination chemistry to that of platinum(II) whose compounds, such as cisplatin and carboplatin, are widely used as antitumor agents. In this context, this work describes the synthesis, characterization and investigation of the antitumor activity of two series of palladium(II) complexes of general formulae [PdX2(HdmIPz)2] {HdmIPz = 3,5-dimethyl-4-iodopyrazole; X = Cl (1), Br (2), I (3), SCN (4)} e [PdX2(HmPz)2] {HmPz =4-methylpyrazole; X = Cl (5), Br (6), I (7), SCN (8)}. The compounds were characterized by elemental analysis, infrared vibrational spectroscopy, 1 H and 13 C{ 1 H} nuclear magnetic resonance, thermogravimetry and differential thermal analysis. The complexes and the free ligands were tested for cytotoxic activity against murine tumor cells. Cisplatin was used as standard drug, being subject to the same conditions. The cytotoxicity of compounds 1-4 was also evaluated towards peritoneal macrophages of mice
Locatelli, Aline. "Síntese, cristalografia e atividade biológica de complexos triazenidos de Au(I), Ag(I), Pd(II) E Pt(II)." Universidade Federal de Santa Maria, 2012. http://repositorio.ufsm.br/handle/1/4237.
Full textThis work presents the synthesis of compounds and their triazenes complexes of gold(I), silver(I), platinum(II) and paladium(II). Triazenes have three nitrogen atoms connected in sequence [ N=N N(H) ] and, when deprotonated, they become excellent ligands in coordination chemistry. The synthesized ligands have ortho nitro substituent and variable substituent halogenated, or also in a position. Characterizations were performed using various techniques: thermogravimetric analysis, ultraviolet and visible spectroscopy, infrared and proton nuclear magnetic resonance, and the main focus of this work was the structural characterization of the complexes by X-ray diffraction on monocrystal, with emphasis the study of these supramolecular arrangements. Nitro and halide substituents (F, Cl, Br and I) providing the formation of various types of interactions, which form supramolecular arrangement. Four ligands were synthesized 1-(2-flurorphenyl)-3-(2-nitrophenyl)triazene (A), 1-(2-chlorophenyl)-3-(2-nitrophenyl)triazene (B), 1-(2-bromophenyl)-3-(2-nitrophenyl)triazene (C), 1-(2-iodophenyl)-3-(2-nitrophenyl)triazene (D) and thirteen complexes {[1-(2-fluorophenyl)-3-(2-nitrophenyl)triazenide](triphenilphosfine)gold(I)} (1), {[1-(2-chlorophenyl)-3-(2-nitrophenyl)triazenide](triphenilphosfine)gold(I)} (2), {[1-(2-bromophenyl)-3-(2-nitrophenyl)triazenide](triphenilphosfine)gold(I)} (3), {trans- bis-[1-(2-chlorophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)paladium(II)} (4), {trans- bis-[1-(2-bromophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)paladium(II)} (5), {trans- bis-[1-(2-iodophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)paladium(II)} (6), {cis- bis-[1-(2-chlorophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)platinum(II)} (7), {cis- bis-[1-(2-bromophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)platinum(II)} (8), {cis- bis-[1-(2-iodophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)platinum(II)} (9), {trans-[1-(2-bromophenyl)-3-(2-nitrophenyl)triazenide]-bis-(pyridine)(chloro)platinum(II)} (10), {cis- [1-(2-bromophenyl)-3-(2-nitrophenyl)triazenide]-ditriphenylphosfine(chloro)platinum(II)} (11), {bis-[1-(2-iodophenyl)-3-(2-nitrophenyl)triazenide]silver(I)} (12) e {[1-(2-fluorophenyl)-3-(2-nitrophenyl)triazenide](triphenylphosfine)silver(I)} (13). For the purpose of Bioinorganic studying the triazenido complexes of gold (I), and Platinum (II) were subjected to evaluation of biological activity shown promising results.
Este trabalho apresenta a síntese de compostos triazenos e seus complexos de ouro(I), prata(I), platina(II) e paládio(II). Os compostos triazenos possuem três átomos de nitrogênio ligados em sequência [ N=N N(H) ]. Quando desprotonados transformam-se em excelentes ligantes com grande exploração na química de coordenação. Os pré-ligantes sintetizados possuem substituinte nitro em posição orto e variável substituinte halogenado, também em posição orto. Foram realizadas caracterizações com diversas técnicas: análise termogravimétrica (TGA), espectroscopia ultravioleta e visível, infravermelho e ressonância magnética nuclear de próton, sendo que o foco principal deste trabalho foi a caracterização estrutural dos complexos por difração de raios-X em monocristal, com destaque no estudo supramolecular destes compostos. Os substituintes nitro e haletos (F, Cl, Br e I) proporcionam a formação de diversos tipos de interações, as quais constituem arranjo supramoleculares. Foram sintetizados quatro pré-ligante 1-(2-fluorfenil)-3-(2-nitrofenil)triazeno (A), 1-(2-clorofenil)-3-(2-nitrofenil)triazeno (B), 1-(2-bromofenil)-3-(2-nitrofenil)triazeno (C), 1-(2-iodofenil)-3-(2-nitrofenil)triazeno (D) e treze complexos {[1-(2-fluorofenil)-3-(2-nitrofenil)triazenido](trifenilfosfina)ouro(I)} (1), {[1-(2-clorofenil)-3-(2-nitrofenil)triazenido](trifenilfosfina)ouro(I)} (2), {[1-(2-bromofenil)-3-(2-nitrofenil)triazenido](trifenilfosfina)ouro(I)} (3), {trans- bis-[1-(2-clorofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)paládio(II)} (4), {trans- bis-[1-(2-bromofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)paládio(II)} (5), {trans- bis-[1-(2-iodofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)paládio(II)} (6), {cis- bis-[1-(2-clorofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)platina(II)} (7), {cis- bis-[1-(2-bromofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)platina(II)} (8), {cis- bis-[1-(2-iodofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)platina(II)} (9), {trans-[1-(2-bromofenil)-3-(2-nitrofenil)triazenido]-bis-(piridina)(cloro)platina(II)} (10), {cis- [1-(2-bromofenil)-3-(2-nitrofenil)triazenido]-ditrifenilfosfina(cloro)platina(II)} (11), {bis-[1-(2-iodofenil)-3-(2-nitrofenil)triazenido]prata(I)} (12) e {[1-(2-fluorofenil)-3-(2-nitrofenil)triazenido](trifenilfosfina)prata(I)} (13). Para fins de estudar a Bioinorgânica dos complexos triazenidos de Ouro(I) e Platina(II), os compostos foram submetidos a avaliação de atividade biológica apresentando resultados promissores.
Broch, Fernanda. "Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II)." Universidade Federal de Santa Maria, 2013. http://repositorio.ufsm.br/handle/1/4248.
Full textTriazenes 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.
Tu, Siyu. "Part I Asymmetric Allylic Alkylation Catalyzed by Pd-Dendron Complexes Part II Self-assembly of n-/p- type Heterojunction Nanomaterials." The Ohio State University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=osu1306946050.
Full textGIOFRE', SABRINA. "SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLIC SYSTEMS OF BIOLOGICAL INTEREST THROUGH DOMINO STRATEGIES." Doctoral thesis, Università degli Studi di Milano, 2020. http://hdl.handle.net/2434/701960.
Full textTiba, Felicia. "Synthesis and kinetic studies of Pd(II), Pt(II) and Ru(II) polypyridine monoaqua complexes." Thesis, 2003. http://hdl.handle.net/10413/3248.
Full textThesis (M.Sc.)-University of Natal, Pietermaritzburg, 2003.
Bouchard, Alexanne. "Trifluorométhylthiolation par C-H activation et synthèse d’amines primaires en chimie en flux continu." Thèse, 2018. http://hdl.handle.net/1866/21912.
Full textAlonso, Martinez Luis Michel. "Development of New Radiotracers for PET Imaging of Adrenomedullin and Angiotensin II Type 1 Receptors." Thesis, 2020. http://hdl.handle.net/1866/24600.
Full textAdrenomedullin receptors are highly expressed in human alveolar capillaries and provide a molecular target for imaging the integrity of pulmonary microcirculation. In previous years, the 99mTc-labeled DFH12 derivative (PulmoBind) demonstrated its potential as a SPECT imaging agent of pulmonary hypertension in phase I and II clinical trials. In this work, we aimed to develop a NOTA-derivatized adrenomedullin analog (DFH17), radiolabeled with aluminum fluoride ([18F]AlF), for PET imaging of pulmonary microcirculation. To achieve this goal, highly concentrated [18F](AlF)2+ was produced from purified 18F using a semi-automatic system. Using inexpensive complexation assays with NOTA, optimal conditions at each step of the process were determined facilitating the radiolabeling optimization of DFH17. Furthermore, combining the Al-to-DFH17 1:3 ratio in 50% ethanol as co-solvent, allowed [18F]AlF-DFH17 production in high radiochemical and chemical purities. PET/CT and biodistribution demonstrated high [18F]AlF-DFH17 lung-to-background ratio and in vivo stability in rats, dog and primate. Contrasted inter-species uptake in the lungs associated with variations of RAMP2 were also detected by PET imaging. Considering high lung uptake, in vivo stability and favorable dosimetry observed in the monkey, the novel AM derivative [18F]AlF-DFH17 exhibits an excellent potential as a PET tracer of human AM receptors. Alterations of the expression levels of AT1R has been linked to cardiac and renal diseases, such as cardiac and renal failures, hypertension and some type of cancers. Previously, [11C]methyl-Candesartan displayed potential for PET imaging of AT1Rs, but a high proportion of PET signal corresponded to non-specific binding from a 11C-labeled hydrophobic metabolite. In this work, the main objective was to develop the novel derivative [18F]fluorobenzyl-Candesartan, with potentially better metabolic profile and biodistribution, using 4-[18F]fluoroidobenzene ([18F]FIB) as prosthetic group. To pursue this goal, radiofluorination parameters such as solvent, amount of precursor, type of catalyst and temperature were optimized to reliably synthesize [18F]FIB in high yield and purity. Coupling of [18F]FIB to the alkyne-trityl-Candesartan was evaluated using the Sonogashira cross-coupling reaction followed by an acid deprotection. After studying several Pd-cross-coupling conditions, the radioconversion yield was slightly increased by means of a Pd(PPh3)4/CuI catalyst and K2CO3 as base in DMF. Therefore, the best reaction conditions for [18F]FIB fluorination and its coupling to alkyne-Candesartan followed by an acid hydrolysis, was fully automated for Synthra® RNPlus Research synthesis module. In general, the synthesis of [18F]FB-Candesartan was achieved in low yields and molar activities due to the formation of structurally-close by-product(s) with similar HPLC retention time. Additional studies to further improve the yield, HPLC purification and molar activity (MA) have been unsuccessful. Other experiments will need to be performed to this end. In conclusion, the use of Sonogashira cross-coupling reaction to produce [18F]FB-Candesartan in high yields and molar activities was found to be challenging.