An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy
Contribuinte(s) |
UNIVERSIDADE DE SÃO PAULO |
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Data(s) |
20/10/2012
20/10/2012
2011
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Resumo |
The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with FAPESP[00/11443-0] Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) FAPESP[06/57577-4] CNPq Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) CAPES |
Identificador |
REACTION KINETICS MECHANISMS AND CATALYSIS, v.102, n.1, p.49-65, 2011 1878-5190 http://producao.usp.br/handle/BDPI/31791 10.1007/s11144-010-0257-0 |
Idioma(s) |
eng |
Publicador |
SPRINGER |
Relação |
Reaction Kinetics Mechanisms and Catalysis |
Direitos |
restrictedAccess Copyright SPRINGER |
Palavras-Chave | #Olefin metathesis #ROMP #7-Oxanorbornene #Ruthenium #Organic acids #RUTHENIUM TRICHLORIDE #NORBORNENE #OXIDATION #COMPLEXES #POLYMERS #MICROSTRUCTURE #CATALYSTS #MECHANISM #KINETICS #Chemistry, Physical |
Tipo |
article original article publishedVersion |