The Reactions of Magnesium Octaethylporphyrin and its π-Cations with Nitrogen Dioxide and Nitrite
Johnson, E.C. and David Dolphin
Reaction of the electrochemically prepared π-cation radical of Mg octaethylporphyrin [Mg(II)OEP] with NaNO2resulted in its reduction and gave, after demetalation, a quantitative yield of OEP. Similar treatment of the corresponding π -dication with NaNO2 gave initial reduction to [Mg(II)OEP]+. followed by partial demetalation and meso nitration. Those latter results are interpreted in terms of [Mg(II)OEP]2+ possessing a potential high enough to effect initial oxidation of the NO2- moiety to NO2, since treatment of [Mg(II)OEP]+ with NO2 resulted in demetalation and formation of mono-, di-, tri-, and tetranitro derivatives of OEP. Thus the reaction observed by G. H. Barnett and K. M. Smith (1974) involved the oxidation of NO2- to NO2, by iodine in MeOH, followed by reaction of the NO2 with either Mg(II)OEP or [Mg(II)OEP]+.