ABSTRACT
The catalytic properties of a series of novel chromium(iii) salophen complexes having different pyridinium chloride units (pyridinium, 2,6-dimethylpyridinium or 4-(dimethylamino)pyridinium ones) have been studied in the reaction of carbon dioxide cycloaddition to phenyl glycidyl ether. The examined complexes were found to be capable of catalyzing cycloaddition under relatively mild reaction conditions without any additional nucleophilic co-catalyst. However, their catalytic activity depended strongly on the structure and number of pyridinium salt units in the ligand molecule. The complex with a single unit of 4-(dimethylamino)pyridinium chloride turned out to be the most active among the examined ones. A TOF of up to 1480 h-1 was obtained in the presence of this catalyst under the following conditions: 120 °C, 2 h, 6 bar, 0.05 mol% (74% epoxide conversion, and >99% selectivity). The most active complex has also been examined as a catalyst in the reactions of CO2 with a series of ten other terminal epoxides. High catalytic activity (TOF = 220-5045 h-1) was observed in most cases, except for the reaction of CO2 with allyl glycidyl ether.
ABSTRACT
Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF6 and working in TBAClO4 and TBABF4. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films.
Subject(s)
Electrolytes , Polymers , Electrochemistry , Ethylenediamines , Kinetics , Oxidation-ReductionABSTRACT
The effect of ligand structure on the catalytic activity of amine-bis(phenolate) chromium(III) complexes in the ring-opening copolymerization of phthalic anhydride and a series epoxides was studied. Eight complexes differing in the donor-pendant group (R1) and substituents (R2) in phenolate units were examined as catalysts of the model reaction between phthalic anhydride and cyclohexane oxide in toluene. They were used individually or as a part of the binary catalytic systems with nucleophilic co-catalysts. The co-catalyst was selected from the following organic bases: PPh3, DMAP, 1-butylimidazole, or DBU. The binary catalytic systems turned out to be more active than the complexes used individually, and DMAP proved to be the best choice as a co-catalyst. When the molar ratio of [PA]:[epoxide]:[Cr]:[DMAP] = 250:250:1:1 was applied, the most active complex (R1-X = CH2NMe2, R2 = F) allowed to copolymerize phthalic anhydride with differently substituted epoxides (cyclohexene oxide, 4-vinylcyclohexene oxide, styrene oxide, phenyl glycidyl ether, propylene oxide, butylene oxide, and epichlorohydrin) within 240 min at 110 °C. The resulting polyesters were characterized by Mn up to 20.6 kg mol-1 and narrow dispersity, and they did not contain polyether units.
ABSTRACT
Platinum electrodes were modified with polymers of the (±)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediaminenickel(II) ([Ni(salcn)]) and (±)-trans-N,N'-bis(3,3'-tert-Bu-salicylidene)-1,2-cyclohexanediaminenickel(II) ([Ni(salcn(Bu))]) complexes to study their electrocatalytic and electroanalytical properties. Poly[Ni(salcn)] and poly[Ni(salcn(Bu))]) modified electrodes catalyze the oxidation of catechol, aspartic acid and NO2-. In the case of poly[Ni(salcn)] modified electrodes, the electrocatalysis process depends on the electroactive surface coverage. The films with low electroactive surface coverage are only a barrier in the path of the reducer to the electrode surface. The films with more electroactive surface coverage ensure both electrocatalysis inside the film and oxidation of the reducer directly on the electrode surface. In the films with the most electroactive surface coverage, electrocatalysis occurs only at the polymer-solution interface. The analysis was based on cyclic voltammetry, EQCM (electrochemical quartz crystal microbalance) and rotating disc electrode method.
