LAUSR

A five-coordinated {Mn(NO)}6 complex of Mn(II)-porphyrinate, [Mn(TMPP2-)(NO)], 1 {TMPPH2 = 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin}, upon reaction with two equivalents of superoxide (O2-) in THF at -40 °C results in the corresponding MnIII-OH complex [MnIII(TMPP2-)(OH)], 2, via the formation of a putative MnIII-peroxynitrite intermediate. Spectral studies and chemical analysis suggest that one equivalent of superoxide ion is consumed to oxidize the metal center of complex 1 leading to [MnIII(TMPP2-)(NO)]+, while the subsequent equivalent reacts with [MnIII(TMPP2-)(NO)]+ to form the corresponding peroxynitrite intermediate. UV-visible and X-band EPR spectroscopic studies suggest the involvement of a MnIV-oxo species in the reaction, which forms through the O-O bond cleavage of the peroxynitrite moiety with concomitant release of NO2. The formation of MnIII-peroxynitrite is further supported by the well-established phenol ring nitration experiment. The released NO2 has been trapped using TEMPO. It should be noted that in cases of MnII-porphyrin complexes, the reaction with superoxide generally proceeds through a SOD-like pathway where the first equivalent of superoxide ion oxidizes the MnII center and itself is reduced to peroxide (O22-), while the subsequent equivalent of superoxide reduces the MnIII center with the release of O2. In contrast, here the second equivalent of superoxide reacts with the MnIII-nitrosyl complex and follows a NOD-like pathway.