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Master's Dissertation
DOI
https://doi.org/10.11606/D.75.2022.tde-06032023-163619
Document
Author
Full name
Vinícius Gonçalves Luna
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2022
Supervisor
Committee
Lima Neto, Benedito dos Santos (President)
Pereira, José Clayston Melo
Roveda Junior, Antonio Carlos
Title in Portuguese
Síntese, caracterização e estudos cinéticos de complexos inéditos de Ru(II) com ligantes ancilares fosfitos para aplicação em ROMP
Keywords in Portuguese
fosfina
fosfito
ligante ancilar
norborneno
ROMP
rutênio
Abstract in Portuguese
Dois novos complexos de rutênio com ligantes ancilares fosfitos foram desenvolvidos como alternativa para reações de metátese de olefinas, do tipo [RuCl2(PPh3)2(POR3)], onde R = Et ou n-Bu. Observou-se que os espectros eletrônicos desses complexos mudam em função do tempo. Por medidas cinéticas em DCM obteve-se os valores da entalpia de transição (+ 81 kJ.mol-1 ; + 62 kJ.mol-1 ) e entropia (- 44 mol-1 .K-1 ; - 105,4 mol-1 .K-1 ) para os complexos com butil e etil, respectivamente, sugerindo uma isomerização geométrica. Por RMN 31P{H} observou-se reações do complexo precursor [RuCl2(PPh3)3] com os fosfitos P(OnBu)3 e P(OEt)3 em solventes diferentes (CDCl3, tolueno-d8 e CD2Cl2), confirmando as formações dos produtos termodinâmicos. As atividades catalíticas foram realizadas para polimerização via metátese do norborneno em função da temperatura, tempo, razão molar [(Ru)/(NBE)], solvente e presença de ácido como ativador na catálise. Observou-se que a acidez do meio favorece os rendimentos da polimerização, obtendo até 54% de conversão com HCl.
Title in English
Synthesis, characterization and kinetic studies of new Ru(II) complexes with phosphite ancillary ligands for application in ROMP
Keywords in English
ancillary ligand
norbornene
phosphine
phosphite
ROMP
ruthenium
Abstract in English
Two new ruthenium complexes with phosphite ancillary ligands were developed as an alternative for olefin metathesis reactions, of the [RuCl2(PPh3)2(POR3)] type, where R = Et or n-Bu. It was observed that the electronic spectra of these complexes change as a function of time. By kinetic measurements in DCM, the values of transition enthalpy (+ 81 kJ.mol-1 ; + 62 kJ.mol-1 ) and entropy (-44 mol-1 .K-1 ; - 105.4 mol-1 .K-1 ) were obtained for the complexes with butyl and ethyl, respectively, suggesting a geometric isomerization. By 31P{H} NMR, reactions of the precursor complex [RuCl2(PPh3)3] with the phosphites P(OnBu)3 and P(OEt)3 in different solvents (CDCl3, toluene-d8 and CD2Cl2) were observed, confirming the formations of thermodynamic products. Catalytic activities were performed for metathesis polymerization of norbornene as a function of temperature, time, molar ratio [(Ru)/(NBE)], solvent and presence of acid as an activator in catalysis. It was observed that the acidity of the medium favors the polymerization yields, obtaining up to 54% conversion with HCl.
 
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Publishing Date
2023-03-07
 
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