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Master's Dissertation
DOI
https://doi.org/10.11606/D.75.2012.tde-17042012-170048
Document
Author
Full name
Daniele Marcondes Ferreira
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2012
Supervisor
Committee
Lima Neto, Benedito dos Santos (President)
Moreira, Wania da Conceição
González, Eduardo René Pérez
Title in Portuguese
Coordenação a centros de rutênio e polimerização via metátese de um novo monômero-ligante do tipo norborneno-piridina
Keywords in Portuguese
norborneno
piridinas
ROMP
Abstract in Portuguese
O monômero-ligante (3amdpy)2NBE foi sintetizado e caracterizado por análise elementar (CHN), infravermelho e RMN (1H e 13C), tratando-se de um novo ligante quelante que apresenta duas piridinas conectadas ao monômero norborneno via grupos amidas. Esse monômero-ligante foi ligado a um centro de Ru(II)-polipiridínico e o complexo resultante foi caracterizado por análise elementar (CHN), infravermelho, RMN (1H e 13C) e espectrometria de massa como sendo cis-[Ru(bpy)2((3amdpy)2NBE)](PF6)2. O espectro eletrônico do novo complexo apresentou absorção no visível em 460 e 480 nm. Essa bandas são típicas de MLCT com valores de ε na ordem de 104 L cm-1 mol-1. O voltamograma cíclico em CH3CN apresentou um processo redox com potencial de meia-onda de 0,89 V vs Ag/AgCl que é de 60 unidades mais positivo do que o complexo precursor cis- [RuCl2(bpy) 2]. O novo metalo-monômero foi submetido à irradiação a λ= 480 nm, demonstrando ser fotoquimicamente inerte em DMSO, CH3CN, acetona e DMF. A emissão do complexo obtido variou em função do solvente e apresentou maior intensidade de emissão em acetonitrila (λem= 720 nm). A variação do solvente não levou ao deslocamento do máximo de emissão do complexo. O monômero-ligante foi polimerizado via metátese catalisada por catalisador de Grubbs, com 23% de rendimento a 50 °C por 5 min. O polímero foi caracterizado por IV e RMN de 1H. Foi solúvel em água e apresentou um ponto de fusão de 288ºC.
Title in English
Coordination to ruthenium centers and polymerization via metathesis of a new monomer-ligand of type norbornene-pyridine
Keywords in English
norbornene
pyridines
ROMP
Abstract in English
The monomer-ligand (3amdpy)2NBE was synthesized and characterized by elemental analysis (CHN), infrared and NMR (1H and 13C) as a new chelate ligand that features two pyridines connected to the monomer norbornene via amide groups. This monomer-ligand was coordinated to a Ru(II)-polypyridinic center and the resulting complex como sendo cis- [Ru(bpy) 2 ((3amdpy) 2NBE)](PF6)2 was characterized by elemental analysis (CHN), IR, NMR (1H and 13C) and mass spectrometry. The electronic spectrum of the new complex showed absorptions in the visible with bands at 460 and 480 nm. These bands are typical of MLCT with ε values in the order of magnitude of 104 L cm-1 mol-1. The cyclic voltammetry in CH3CN showed a redox process with half-wave potential of 0,89 V vs Ag/AgCl which is ca. 60 units higher than the halfwave potential for the cis-[RuCl2(bpy)2] precursor complex. The new complex was photochemically inert when irradiated at 480 nm either in DMSO, CH3CN, acetone or DMF. The emission of the complex depends on the solvent and presented large emission intensity in acetonitrile (λem = 720 nm). The variation of the solvent does not shift the emission maximum. Ring opening metathesis polymerization of the monomer-ligand (3amdpy)2NBE was carried out at 50 °C for 5 min with 23% of yield using Grubbs type catalyst. The resulting polymer was characterized by IR and NMR-1H. It was water-soluble and showed a melting point of 288°C.
 
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Publishing Date
2012-08-23
 
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