This contribution focusses on the electrochemical and spectroelectrochemical behavior of Fe(T(C6H5)PP)OR (T(C6H5)PP= meso-tetraphenylporphyrin, R = methyl, t-butyl) complexes as compared to previously characterized  Fe(T(p-C6H4CH3)PP)OR'species (T(p-C6H4CH3)PP = tetra(p-tolyl)porphyrin, R' = methyl, ethyl, isopropyl, t-butyl), and their corresponding chlorideprecursors.  The 1H NMR and UV-VIS spectroscopic data for these species are consistent with expectations, e.g. the �-H atoms on the porphyrin ring are paramagnetically broadened and their chemical shifts moved to approximately 83 ppm in saturated CDCl3 solutions.  Cyclic voltammetry studies in rigorously dry solvents and performed in a drybox show that these species are particularly sensitive to the presence of trace amounts of water, and typically form the (por)Fe-(�-O)-Fe(por) species (por = T(C6H5)PP and T(p-C6H4CH3)PP) at the electrode surface after oxidation. The �-oxo dimer species is unusually persistent at the electrode surface, which necessitates stirring of the solution between cyclic voltammetry scans.  The reactivity of these 5-coordinate complexes with nitric oxide will be discussed.

Synthesis, electrochemistry, and spectroelectrochemistry of Fe(T(C6H5)PP)OR complexes, (T(C6H5)PP = meso-tetraphenylporphyrin; R = methyl, t-butyl)

248th National Meeting (2014)

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