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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Síntese e caracterização de complexos de Cu(I), Cu(II) E Au(I) com ligantes triazenidos contendo substituintes triazóis / Synthesis and characterization of Cu(I), Cu(II) AND Au(I) complexes with triazenido ligands containing triazole substituents

Morgan, Dieisson 29 November 2013 (has links)
Triazenido ions are isoelectronic to amidinato anions,[R'N C(R)=NR']- and have a broad versatility in coordination chemistry. Metal complexes including triazenido ligands find applications in various areas of chemistry. Triazenes and complexes including triazole derivatives show extensive applicability as for example in supramolecular chemistry and pharmacological compounds. This work presents deals with the study of new triazene derivatives with triazole substituents resulting from the click reactions, acting as ligands in complexes with Cu(I), Cu(II) and Au(I). The following ligands 1,3-bis(2-azidophenyl)triazene (2), 1-(methyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene-N-oxide (4), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene (5), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazene (6) and, complexes 1,3-bis(2-azidophenyl)triazenide-κN11- triphenylphosphine-gold(I) (2a), bis-{1-(methyl)-3-[2-(4-phenyl-1,2,3-triazole-κN2)]triazenide-1-oxide-κ2N3,O}copper(II) (4b), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (5a), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (6a), bis[1,3-bis(2-(4-phenyl-1,2,3-triazole-κN2)-μ-N3-triazenide]-κN11,κN13 copper(I)κN13,κN11´copper(I) (Cu Cu) (6b) were investigated. The compounds were characterized by IR, UV-Vis and NMR (1H e 13C) spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. Triazene (2) and complex (2a) exhibit intramolecular assembling through classical and non-classical hydrogen bonding. Complexes with Au(I), (2a), (5a) e (6a), the metal atom show linear coordination geometry. The metal atom in complex (6b) shows a T distorted coordination geometry, which is extended to a quadratic coordination resulting from d10 d10 interactions between Cu(I) ions. Triazene (6) and its respective complexes (6a) e (6b) exhibit intermolecular interactions of the type C−H···M. Antibacterial activity of triazene (5) and complex (5a) were assayed resulting to be inactive against the bacteria tested. / Os compostos triazenidos são isoeletrônicos a íons amidinatos [R'NH C(R)=NR'], e têm sido usados com sucesso na química de coordenação. A complexação a íons metálicos possibilita a sua aplicação em diversas áreas da química. Assim como os triazenos, os triazóis possuem vasta aplicabilidade, desde a química supramolecular até a área farmacológica. Este trabalho apresenta o estudo inédito de pré-ligantes triazenos contendo substituintes triazóis os quais foram obtidos a partir de reações de Click, e seus respectivos complexos de Cu(I), Cu(II) e Au(I). Foram sintetizados os pré-ligantes 1,3-bis(2-azidofenil)triazeno (2), 1-(metil)-3-(2-(4-fenil-1,2,3-triazol)triazeno-N-óxido (4), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazeno (5), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazeno (6) e os complexos 1,3-bis(2-azidofenil)triazenido-κN11-trifenilfosfina-ouro(I) (2a), bis-{1-(metil)-3-[2-(4-fenil-1,2,3-triazol-κN2)]triazenido-1-óxido-κ2N3,O}cobre(II) (4b), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (5a), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (6a), bis[1,3-bis(2-(4-fenil-1,2,3-triazol-κN2)-μ-N3-triazenido]-κN11,κN13 - cobre(I)κN13,κN11´cobre(I) (Cu Cu) (6b). Estes foram caracterizados por espectroscopia de IV, UV-Vis e RMN (1H e 13C), espectrometria de massas de baixa ou alta resolução (EI, ESI, ESI(+)-TOF e ESI(-)-TOF) e difração de raios X em monocristal. O triazeno (2) e complexo (2a) apresentam ligações de hidrogênio intermoleculares e intramoleculares do tipo clássica e não-clássica. Os complexos de Au(I), (2a), (5a) e (6a) possuem geometria de coordenação linear. O complexo (6b) apresenta uma geometria T distorcida, a qual é estendida para quadrática pela interação d10 d10 entre os átomos de Cu(I), o triazeno (6) e seus complexos (6a) e (6b) apresentam ainda ligações intermoleculares do tipo C−H···M. Foi testada a atividade antibacteriana do triazeno (5) e o complexo (5a), os quais mostraram-se inativos frente às bactérias testadas.

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