Narrow Results

TPPMnOAc and four different kinds of manganese tetraphenylporphyrin acetates were synthesized using different numbers of methoxy substituents in various positions of the phenyl rings. These porphyrins were used as catalysts in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n-Bu₄NHSO₅) as the oxidant and imidazole as the axial base. The following order of catalytic activity was obtained: TPPMnOAc ≥ T(2,3-OMeP)PMnOAc > T(4-OMeP)PMnOAc > T(3,4-OMeP)PMnOAc > T(2,4,6-OMeP)PMnOAc. By studying the UV-vis spectra in the reaction solution, the stability of the applied methoxy porphyrins and the effect of this factor on obtained yields were investigated. Lower catalytic activity in some of the methoxy porphyrins emphasized steric effects and special hydrogen bonding among the reaction elements. However, the stability of T(2,3-OMeP)PMnOAc under our reaction condition was considerable and high activity was observed. By adding small amounts of alcohol to the reaction solution, the effect of the solvent mixture was previewed and steps were taken to identify the active intermediate of the catalyst in these conditions.

Mn(III)-tetra phenyl porphyrin-acetate (MnTPPOAc) and some kinds of meso-phenyl substituted porphyrins by hydroxyl groups and their Mn(III) complexes were synthesized. These Mn-porphyrins were used as catalyst in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n-Bu₄NHSO₅) as oxidant and tetra-n-butylammonium acetate (n-Bu₄NOAc) as the axial ligand. The following order of catalytic activity was observed for cyclooctene: T(2,3-OHP)PMnOAc ≫ T(2,4,6-OHP)PMnOAc ≥ T(4-OHP)PMnOAc ≥ T(2,6-OHP)PMnOAc ≥ TPPMnOAc and T(2,3-OHP)PMnOAc ≫ TPPMnOAc > T(4-OHP)PMnOAc > T(2,4,6-OHP)PMnOAc > T(2,6-OHP)PMnOAc for other alkenes. Different activity and stability of the catalysts were interpreted based on the hydrogen bonding between hydroxyl groups with appropriate orientation on the meso-position of the phenyl groups and axial bases or oxidant. T(2,3-OHP)PMnOAc catalyst has shown optimal condition for effective hydrogen bonding. In the case of other catalysts, electronic and steric factors overcome the hydrogen bonding effect.

Dithionite can be used to reduce Fe(II) and produce nanoscale zero-valent iron (nZVI) under conditions of high pH and in the absence of oxygen. The nZVI is coprecipitated with a sulfite hydrate in a thin platelet. The nanoparticles formed are not pure iron but this feature does not appear to affect their degradation performance under air or N₂ gas conditions. The efficiency of trichloroethylene (TCE) degradation, when one is employing nanoparticles manufactured using dithionite (nZVI_S2O4), is similar to if not slightly better than that of the more conventional borohydride procedure (nZVI_BH4). The other advantages of the dithionite method are that (i) it uses a less expensive and widely available reducing agent, and (ii) there is no production of potentially explosive hydrogen gas. Oxidation of benzoic acid using the nZVI_S2O4 particles results in different byproducts than those produced when nZVI_BH4 particles are used. The low oxidant yield based on hydroxybenzoic acid generation is offset by the production of higher concentrations of phenol. The high concentration of phenol compared to hydroxybenzoic acids suggests that OH^• addition is not the primary oxidation pathway when one is using the nZVI_S2O4 particles. It is proposed that sulfate radicals () are produced as a result of hydroxyl radical attack on the sulfite matrix surrounding the nZVI_S2O4 particles, with these radicals oxidizing benzoic acid via electron transfer reactions rather than addition reactions.