Isolation of an oxomanganese(v) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H₂O₂ in aqueous solution

The reaction of [Mn(TF₄TMAP)](CF₃SO₃)₅ (TF₄TMAP = meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H₂O₂ (2 equiv) at pH 10.5 and 0°C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-l-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H₂¹⁸O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF₄TMAP)]⁵⁺ with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H₂O₂ depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on ¹⁸O incorporation from H₂¹⁸O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF₄TMAP)]⁵⁺ and KHSO₅ in buffered H₂¹⁸O solutions. A high proportion of ¹⁸O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.