Corroles with group 15 ions. 2. Synthesis and characterization of octaethylcorroles containing a phosphorus central atom

The synthesis, spectroscopic characterization, and electrochemistry of five new phosphorus corroles are reported. The investigated complexes contain a lkyl, aryl, ore, or hydride axial ligands and are represented as (OEC)P(H)( 2) (OEC)P(CH3)(2), (OEC)P(C6H5)(2), (OEC)P=O, and [(OEC)P(CH3)]+ClO4-, wher e OEC is the trianion of octaethylcorrole. The products of electrooxidation and/or electroreduction were also characterized by UV-vis and ESR spectros copy. Correlations are shown to exist between reversible half-wave potentia ls for the first oxidation and first reduction of each compound and the com bined electronegativity of the central ion and the axial ligand(s). The ele ctrochemical HOMO-LUMO gap, defined as the difference between first reducti on and first oxidation, was found to be independent of the electron-transfe r site and similar in magnitude to the value generally observed for metallo porphyrins with planar macrocycles, i.e., 2.25 +/- 0.15 V.