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(TF(4)TMAP)](CF(3)SO(3))(5) (TF(4)TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H(2)O(2) (2 equiv) at pH 10.5 and 0 degrees 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-1-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H(2) (18)O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](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 H(2)O(2) 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 (18)O incorporation from H(2) (18)O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)](5+) and KHSO(5) in buffered H(2) (18)O solutions. A high proportion of (18)O 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.
Nam
Wonwoo
W
Department of Chemistry and Division of Molecular Life Sciences, Ewha Womans University Seoul, Korea. wwnam@ewha.ac.kr
Kim
Inwoo
I
Lim
Mi Hee
MH
Choi
Hye Jin
HJ
Lee
Je Seung
JS
Jang
Ho G
HG
D002220:Carbamazepine / Q000031:analogs & derivatives / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008345:Manganese / Q000737:chemistry*; D008652:Mesoporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D016877:Oxidants / Q000737:chemistry; D010100:Oxygen / Q000378:metabolism*; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*
D008652:Mesoporphyrins; D016877:Oxidants; D012996:Solutions; D014867:Water; D002220:Carbamazepine; D008345:Manganese; D006861:Hydrogen Peroxide; D010100:Oxygen