ELECTROCHEMICAL AND SPECTROSCOPIC CHARACTERIZATION OF MANGANESE(III) DODECAPHENYLPORPHYRIN DERIVATIVES AND X-RAY STRUCTURAL DETERMINATION OF 12,13,17,18-OCTAPHENYLPORPHYRINATO)-MANGANESE(III) - FORMATION OF A MANGANESE(IV) SPECIES BY OZONE AND ELECTROCHEMICAL OXIDATION

The electrochemistry of nine different manganese(III) dodecaphenylporp hyrins containing halogen or CF3 groups on the phenyl rings of the por phyrin macrocycle is reported. Six of the compounds were previously sy nthesized while three of the derivatives, (DPPF8)MnCl, (DPPCl12)MnCl a nd (DPPF28)MnCl, are reported for the first time in this study. Each o f the nine compounds was characterized in its neutral form by UV-visib le and H-1 and F-19 NMR spectroscopy and in its singly oxidized form b y UV-visible and ESR spectroscopy after reaction with ozone. An X-ray crystal structure of (DPPF20)MnCl (C92H40N4F20MnCl . 2CHCl(3) . 0.25H( 2)O) was also obtained. The compound crystallized in the monoclinic sp ace group P2(1)/c with cell dimensions a = 17.258(3) Angstrom, b = 28. 593(6) Angstrom, c = 17.476(4) Angstrom, beta = 107.16(2)degrees, and Z = 4. Tt is nonplanar and adopts a saddle/ruffle hybridized macrocycl e conformation.