10.1246/bcsj.65.23
The research investigates the redox behaviors of high-spin (10,20-diaryletioporphyrinato Il) iron(III) complexes through cyclic voltammetry in dichloromethane. The study examines whether the redox waves are due to porphyrin-ring-centered reactions or metal-centered reactions by analyzing spectroelectrochemical results and Hammett reaction constants. Key chemicals involved in the research include 10,20-Diaryletioporphyrin II (DAEPH2), which is used as a ligand for systematic electrochemical investigations due to its stability and solubility in organic solvents. Iron(III) complexes such as DAEPFeCl, DAEPFeOAr, and (DAEPFe):O4 are prepared and studied for their redox properties. Other chemicals like tetrabutylammonium perchlorate (TBAP) serve as the supporting electrolyte, and phenol derivatives are used in the preparation of phenoxide coordinated complexes. The research aims to elucidate the redox behavior of these metalloporphyrins, which is important for both biochemical and synthetic applications.
10.1021/jo00269a037
The research focuses on the electrochemical oxidation of dipyrrolic compounds, specifically pyrromethanes, pyrromethenes, and pyrroketones, which are valuable intermediates in the organic synthesis of porphyrins. The purpose of the study was to evaluate the electron availability and chemical reactivity of these compounds through cyclic voltammetry and to determine whether substituent partial potentials previously established for monopyrroles could be applied to predict the experimental data for these more complex dipyrrolic systems. The researchers measured the oxidation potentials of various dipyrrolic compounds in acetonitrile and found that, in most cases, the observed potentials closely matched the calculated values based on the substituent partial potentials of the composite pyrroles. However, exceptions were noted for pyrromethanes with a terminal α-methyl group, which showed significant deviations. The study concluded that the electrochemical oxidation of pyrromethanes typically involves a two-electron process, leading to the formation of pyrromethene salts, and that the oxidation potentials of pyrromethenes are higher than those of pyrromethanes, with the potentials of pyrroketones being even higher due to the electron-withdrawing nature of the central carbonyl function. The chemicals used in the process included various substituted pyrromethanes, pyrromethenes, and pyrroketones, acetonitrile as the solvent, and tetrabutylammonium perchlorate as the supporting electrolyte.
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