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Master's Dissertation
DOI
https://doi.org/10.11606/D.75.2019.tde-12112019-174904
Document
Author
Full name
Eliada Andrade da Silva
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2019
Supervisor
Committee
Lima Neto, Benedito dos Santos (President)
Bogado, André Luiz
Júnior, Valdemiro Pereira de Carvalho
Metzker, Gustavo
Title in Portuguese
Desenvolvimento de complexos de rutênio com combinações de ligantes ancilares para polimerização via metátese de olefinas cíclicas: trifenilfosfina com tri-n-butilfosfina e p-cimeno com aminas cíclicas
Keywords in Portuguese
aminas
catalisadores
complexos de rutênio
fosfinas
metátese
ROMP
Abstract in Portuguese
Os complexos precursores [RuCl2(PPh3)3] e [Ru(p-cimeno)Cl2]2, sendo o complexo [RuCl2(PPh3)3] já conhecido da literatura foi devidamente sintetizado para a síntese com o ligante, tri-n-bultifosfina (PnBu3), dando origem ao complexo [RuCl2(PPh3)(PnBu3)2] 2. O precursor [Ru(p-cimeno)Cl2]2 foi adquirido de forma comercial, e juntamente com os ligantes pirrolidina, piperidina e peridroazepina deram origem aos novos complexos 3, 4 e 5. Todos os complexos inéditos foram sintetizados com o intuito de estuda-los como catalisadores de reações de polimerização de olefinas cíclicas via metátese por abertura de anel - ROMP (ring opening metathesis polymerization). Esse estudo é baseado a partir da atividade catalítica destes complexos, quando se variam os ligantes ancilares nas esferas de coordenação, discutindo os resultados em termos de caráter doador-σ e impedimento estérico dos ligantes. Os novos complexos do tipo [RuCl2(PnBu3)n(L)m] e [RuCl2(p-cimeno)n(L)m] foram caracterizados por análise elementar de CHN, espectroscopia de massas, espectroscopia na região do ultravioleta-visível (UV-Vis), espectroscopia vibracional na região do Infravermelho (FTIR), ressonância paramagnética eletrônica (EPR), ressonância magnética nuclear de 1H e 13C e voltametria cíclica. Para os complexos 3, 4 e 5, foram realizados estudos cinéticos a partir do UV-Vis, variando temperatura e concentrações de ligantes, para acompanhar as suas devidas formações. Os experimentos para as reações de ROMP com os complexos 2, 3, 4, e 5 frente aos seus complexos precursores demostraram rendimentos de um modo geral, mais eficiente.
Title in English
Development of ruthenium complexes with combinations of ancillary ligands for ring-opening metathesis polymerization of cyclic olefins: triphenylphosphine with tri-n-butilphosphine and p-cimene with cyclic amines
Keywords in English
amines
catalysis
metathesis
phosphines
ROMP. complexes of ruthenium
Abstract in English
The complexes [RuCl2 (PPh3)3] and [Ru (p-cymene) Cl2],2, the [RuCl2 (PPh3)3] complex being bultiphosin (PnBu3), giving rise to the complex [RuCl2 (PPh3) (PnBu3)2] 2. The precursor [Ru (p-cymene) Cl2]2 was commercially available, and In addition, with pyrrolidine, piperidine and perhydroazepine linkers gave rise to the new complexes 3, 4 and 5. All complexes were synthesized with the aim of this work was to study the catalysts of cyclic olefin polymeriza tion reactions through ring-opening metathesis-ROMP (ring-opening metathesis polymerization). This study is based on the catalytic activity of complexes, when the ancillary coordination spheres are differentiated, discussing the results in terms of donor- σ characteristics and steric hindrance of the ligands. The new complexes of type [RuCl2 (PnBu3) n (L) m] and [RuCl2 (p-cymene) n(L) m] were characterized by elemental CHN analysis, mass spectroscopy, ultraviolet-visib le spectroscopy UV-Vis), Infrared Vibrational Spectroscopy (FTIR), Nuclear Magnetic Resonance (EPR), 1H and 13C (1H) nuclear magnetic resonance and cyclic voltammetry. For complexes 3, 4 and 5, the UV-Vis side effects, temperature variation and concentrations of binders were observed to follow as their proper formations. Experiments for the ROMP keys with complexes 2, 3, 4, and 5 compared to their precious precursors have generally proved to be more efficient results.
 
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Publishing Date
2019-12-12
 
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