Journal Name: Reaction Kinetics, Mechanisms and Catalysis

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 RuIII compounds: the consumption of RuIII species in the presence of carboxylic acids monitored by ESR spectroscopy

Journal name: Reaction Kinetics, Mechanisms and Catalysis

Author names: Nouga C. Batista  José L. Silva Sá  Bruce R. McGarvey  Douglas W. Franco  Benedito S. Lima-Neto ()

Affiliation of the corresponding author: Instituto de Química, Universidade de São Paulo, C. P. 780, 13560-980, São Carlos, SP, Brazil

E-mail address of the corresponding author:

Fig. S1Dependence of the intensity of the ESR signal onthe [Ru(NH3)5H2O]3+ ion concentration in 20%-H2O/EtOH, at 25.0 oC

Fig. S2 Overplots of theESR spectra as a function of time for the aqueous ROMP of the diacid monomer with K2[RuCl5H2O] in 50%-EtOH/H2O at 50oC; [Ru]o = 6.3 mmol L-1,[monomer]o = 1.7 mol L-1

Fig. S3 Overplots of theESR spectra as a function of time for the aqueous ROMP of the diacid monomer with RuCl3 in 50%-EtOH/H2O at 50oC; [Ru]o = 6.3 mmol L-1, [monomer]o = 1.7 mol L-1

Fig. S4 Monomer consumption as a function of time monitored by 13C NMR for the aqueous ROMP of the diacid monomer with RuCl3, in 50%-H2O/EtOH at 50.0  0.1 oC;[Ru]o = 40 mmol L-1, [monomer]o = 2.4 mol L-1. Insert: reciprocal of monomer concentration vs. reaction time

Table S1 Polymerization yield determined by gravimetry for the aqueous ROMP with RuCl3 as a function of time, in 50%-H2O/EtOH at 50  1 oC

Entry / Reaction time / h / Yielda / %
1. / 1 / 2.0
2. / 2 / 40
3. / 3 / 50
4. / 4 / 54
5. / 7 / 52
6. / 10 / 53

a Average values from two independent experiments;[monomer]o = 2.0 mol L-1; [Ru]o = 10 mmol L-1