Fiber-Optic Infrared Spectroelectrochemical Studies of Six-Coordinate Manganese Nitrosyl Porphyrins in Nonaqueous Media

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The redox behavior of the six-coordinate (por)Mn(NO)(1-MeIm) (por = tetraphenylporphyrin dianion (TPP), tetratolylporphyrin dianion (TTP), or tetra-p-methoxyphenylporphyrin dianion (T(p-OMe)PP)) complexes were examined by cyclic voltammetry at room temperature and at -78 degrees C in two nonaqueous solvents (CH2Cl2 and THF) at a Pt disk electrode. In CH2Cl2 at room temperature, the compounds undergo four oxidations and two reductions within the solvent limit; in THF, the compounds undergo one oxidation and three reductions. In both solvents, the first oxidation represents a chemically irreversible one-electron process involving the rapid loss of nitric oxide. The oxidation occurs at the MnNO site as judged from bulk electrolysis, UV-vis spectroscopy at room temperature, and IR spectroelectrochemistry at room temperature and at -78 degrees C. The second oxidation, accessible in CH2Cl2, is also chemically irreversible and occurs at the porphyrin ring; the third and the fourth oxidations are, on the other hand, chemically reversible but also occur at the porphyrin ring. The first reduction is chemically irreversible in CH2Cl2, occurs at the porphyrin ring, and is followed by loss of NO. In THF, the first reduction is chemically reversible and is followed by reversible loss of NO.