An analysis was given for the temperature dependence of the effective first-order rate constants determining the kinetics of the oxidation of 1-hexene by the O2-TPPMnCl-NaBH4 catalytic system in the presence of a neutral salt at long reaction times and related to catalyst destruction processes.

Manganese(III) in its tetraphenylporphyrinate complex may be reduced to manganese(II) using hydrogen passed through a palladium alloy membrane.

It has been established that Co(II) porphyrins form five-coordinated complexes with olefins having a high level of donor capability, and six-coordinated complexes in the presence of oxygen. For these systems, we have found the equilibrium constants and the rate constant for the forward reaction of formation of the six-coordinated complex with oxygen in the example of 2-methyl-1-butene.

The rate and extent of oxidation of olefins by molecular oxygen activated by a tetraphenylporphyrin complex of divalent manganese is directly related to the degree of substitution of the double bond. Δ5-Steroids are oxidized to 5α-hydroxysteroids, and this reaction provides a convenient method for the preparation of these steroids.

The main results of the present study confirm the ideas previously proposed by us to explain electric field effects in ionic polymerization, namely, that they are mainly caused by space distribution of the ions present in the system at the moment of field application. Polymerization of 1,3-dioxolane by SnCl4, (C2H5)2- OBF3, and (C6H5 ) 3 CSbF6 and also of styrene by (C6H5)3CSbF6 was studied. The ratios of the rate constants of free ions and ion pairs and approximate values of the constants were calculated. The possibility of secondary initiation in the system styrene-(C6H5)3 CSbF6 was found, probably due to the discharge of SbF6 counter ion at the anode. The data show that a transition to a new polymerization rate occurs in a definite time period dependent on the velocity of the space distribution of counter ions or ions of both signs. This fact makes it possible to treat the proposed method of the analysis of electric field effects in polymerization kinetics as a relaxational one.

Investigations were made which show that the change in the dynamics of polymerization and in molecular weight of the polymer under an electric field is connected with the redistribution of the ions growing macromolecules and counterions. Analysis of the equations obtained showed that the field can either increase or decrease the rate of the process. The effect's trend and magnitude depend on the ratio of the mobilities of macroions and counterions, degree of dissociation of active centers, and the ratio of rate constants of free ions and ion pairs. An analysis of literature data relevant to polymerization under an electric field was made.