A nitrosyl complex of Mn-porphyrinate, 1 has been synthesized and characterized. It was found to donate a nitroxyl anion (NO) to suitable acceptors in dichloromethane solution in the presence of visible light. The evolution of NO and the characteristic reaction with PPh in the presence of H confirms the NO/HNO donation.
View Article and Find Full Text PDFA Co(II) complex, [Co(L)(HO)](ClO), 1, having a bidentate ligand L [L = bis(3,5-dimethylpyrazolyl)methane] has been synthesized. Complex 1 in acetonitrile solution at -40 °C, in the presence of HO and NEt, afforded the corresponding Co(III)-peroxo species, [Co(L)(O)], as the transient intermediate 1a. Thermal instability precluded its isolation and further characterization.
View Article and Find Full Text PDFA five-coordinated {Mn(NO)} complex of Mn(II)-porphyrinate, [Mn(TMPP)(NO)], 1 {TMPPH = 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin}, upon reaction with two equivalents of superoxide (O) in THF at -40 °C results in the corresponding Mn-OH complex [Mn(TMPP)(OH)], 2, the formation of a putative Mn-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 [Mn(TMPP)(NO)], while the subsequent equivalent reacts with [Mn(TMPP)(NO)] to form the corresponding peroxynitrite intermediate. UV-visible and X-band EPR spectroscopic studies suggest the involvement of a Mn-oxo species in the reaction, which forms through the O-O bond cleavage of the peroxynitrite moiety with concomitant release of NO.
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