The kinetics of disproportionation of hydrogen peroxide in the presence of palladium(II)porphyrins with regularly changing macroring structures
                                
                                    
                                        作者:T. N. Lomova、M. E. Klyueva、O. V. Kosareva、M. V. Klyuev                                    
                                    
                                        DOI:10.1134/s0036024408070066
                                    
                                    
                                        日期:2008.7
                                    
                                    The kinetics and spectral manifestations of alkaline decomposition of H2O2 in a water-dimethylformamide medium catalyzed by (PdP)-P-II (P is the dianion of octaethylporphyrin and its monophenyl, 5,15-diphenyl,5,10-diphenyl, triphenyl, and tetraphenyl derivatives substituted at meso positions) was studied over a wide range of reagent concentrations under polythermal conditions. A complete kinetic description of the reacting systems was given, and the rates and set of elementary reactions, intermediate compounds, and kinetically significant equilibria were determined. The ion-molecular mechanism of hydrogen peroxide decomposition was substantiated. According to this mechanism, the only stable radicals involved in the reaction are the pi radical cation forms of palladium(II)porphyhrin catalysts.