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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

cis-[RuIICl2(dppb)(bipy)]cis complex immobilized in SBA-15: development of new materials / ImobilizaÃÃo do complexo cis-[RuIICl2(dppb)(bpy)] na matriz sÃlida SBA-15: desenvolvimento de novos materiais

Aldenor Souza de Oliveira 15 February 2013 (has links)
CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Este trabalho foi realizado com o objetivo principal de acrescentar informaÃÃes cientÃficas sobre a imobilizaÃÃo de complexos metÃlicos em matrizes sÃlidas, propondo uma ligaÃÃo covalente entre o complexo cis-[RuIICl2(dppb)(bipy)] e a matriz sÃlida mesoporosa Santa BÃrbara Amorphus (SBA-15). Para a imobilizaÃÃo do complexo por ligaÃÃo covalente, utilizou-se como estratÃgia o âGraftingâ(encherto) da matriz sÃlida com grupos bipiridinÃcos, a partir da reaÃÃo entre o agente sililante 3-aminopropiltrietÃxisilano(3-APTES), o ligante 4,4â- (clorocarbonil)-2,2â-bipiridina(Cl-bpy) e a matriz SBA-15, obtendo-se o sÃlido SBA-4,4â-bis(clorocarbonil)-2,2â-bipiridina-bis[(3-trietoxisililpropil)amida](SBA-bpy). Posteriormente, o complexo [RuIICl2(dppb)PPh3] foi adicionado ao composto SBA-bpy obtendo-se o novo sÃlido SBA-[RuIICl2(dppb)(bpy)] (SBA-bpy-RuCl). O novo composto sintetizado foi submetido à tÃcnicas de caracterizaÃÃo espectroscÃpicas, termogravimÃtricas, adsorÃÃo e desorÃÃo de N2 e estudo eletroquÃmico. Os resultados de FTIR, apresentam indÃcio da ligaÃÃo entre o agente sililante 3-APTES e o ligante Cl-bpy, e, os espectros de 29Si-CP/NMR- MAS e 13C-CP/NMR- MAS confirmam a interaÃÃo quÃmica entre as espÃcies SBA-15, 3-APTES e Cl-bpy bem como a formaÃÃo da espÃcie SBA-bpy-RuCl. Os espectros de UV-vÃs e o estudo eletroquÃmico apresentam sinais da formaÃÃo do complexo [RuIICl2(dppb)(bpy)] e os resultados de BET confirmam a presenÃa deste complexo no interior da matriz sÃlida. A reatividade do complexo imobilizado foi inicialmente verificada com a utilizaÃÃo das molÃculas de prova NCS- e CO para obter as espÃcies SBA-bpy-RuNCS e SBA-bpy-RuCO. A interaÃÃo destas molÃculas mostra a disponibilidade de sÃtios ativos no centro metÃlico do complexo imobilizado, propriedade esta que à fundamental para a manutenÃÃo da atividade catalÃtica do complexo, bem como a possibilidade da obtenÃÃo de novos compostos e da captura de gases nocÃvos, tais como o CO. / This study was conducted with the primary goal to add scientific information on the immobilization of metal complexes on solid matrices, suggesting a covalent bond between the complex cis-[RuIICl2(dppb) (bipy)] and mesoporous solid matrix Santa Barbara Amorphous (SBA-15). For the immobilization of the complex by covalent bonding, the solid matrix was initially subjected to a "Grafting" with bipyridyl groups from the reaction between silylating agent 3 - aminopropyltriethoxysilane (3 - APTES), the ligand 4,4 ' - (chlorocarbonyl) - 2,2 ' - bipyridine (bpy Cl-) and the array SBA - 15 for the species SBA - 4, 4' - bis (chlorocarbonyl) - 2,2' - bipyridine - bis [(3 - trietoxisililpropil ) amide] (SBA - bpy). Subsequently, the complex [Ru II Cl 2 (dppb) PPh 3 ] was added to compound SBA - bpy obtaining the new species SBA - [Ru II Cl 2 (dppb) (bpy)] (RuCl - SBA - bpy). The new synthesized compound was subjected to spectroscopic characterization techniques, thermogravimetry, adsorption and desorption of N 2 and electrochemical study. The results of FTIR, show evidence of linkage between the silylating agent and the binder APTES 3 - Cl - bpy, and spectra 29 Si - CP/NMR - MAS and MAS 13 C - CP/NMR - confirm the co - condensation between the species SBA - 15, 3 - APTES and Cl - bpy well as formation of species SBA - bpy - RuCl. The UV - Vis spectra and electrochemical study show signs of complex formation [Ru II Cl 2 (dppb) (bpy)] and BET results confirm the presence of this complex within the solid matrix. The reactivity of immobilized complex was first verified using the test molecules NCS-and CO to form both species SBA - bpy RuNCS - and SBA - bpy - RuCO. The interaction of these molecules shows availabl e active sites at the metal center of the complex, this property is essential for maintaining the catalytic activity of the complex, and the possibility of obtaining novel compounds and the capture of harmful gases, such as CO.

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