The electrochemical and spectroelectrochemical behavior of Fe(T(p-C6H4Cl)PP)OR complexes (T(p-C6H4Cl)PP= meso-tetra(p-chlorophenyl)porphyrin, R = methyl, t-butyl) is compared to previously characterized Fe(T(p-C6H4OCH3)PP)OR' species (T(p-C6H4OCH3)PP = tetra(p-methoxyphenyl)porphyrin, R' = methyl, ethyl, isopropyl) and their corresponding chloride precursors. The chemistry of the electron-rich T(p-C6H4OCH3)PP complexes and the less electron rich T(p-C6H4Cl)PP complexes will be compared. The 1H NMR and UV-VIS spectroscopic data for these species are consistent with expectations based on their magnetic properties and the electron-richness of the porphyrin ligands. Cyclic voltammetry studies in rigorously dry solvents and performed in a drybox show that these species are sensitive to the presence of trace amounts of water, and typically form the (por)Fe-(�-O)-Fe(por) species (por = T(pC6H4OCH3)PP and T(p-C6H4CH3)PP) at the electrode surface after 1-electron oxidation. The oxidations appear reversible (E�' ~ 1 V vs ferrocene in CH2Cl2/ 0.1M NBu4PF6) at moderately fast scan rates (>0.8 V/s) without follow-up chemistry. The reactivity of the 5-coordinate Fe(T(p-C6H4Cl)PP)OR complexes with nitric oxide will be discussed.

Synthesis, electrochemistry, and spectroelectrochemistry of Fe(T(p-C6H4Cl)PP)OR complexes, (T(p-C6H4Cl)PP = meso-tetra(p-chlorophenyl)porphyrin; R = methyl, t-butyl)

248th National Meeting (2014)

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