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


Autoria(s): BATISTA, Nouga C.; SA, Jose L. Silva; MCGARVEY, Bruce R.; FRANCO, Douglas W.; LIMA-NETO, Benedito S.
Contribuinte(s)

UNIVERSIDADE DE SÃO PAULO

Data(s)

20/10/2012

20/10/2012

2011

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

http://dx.doi.org/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