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[15] In the absence of an olefin substrate, the intermediate 1 decayed
slowly to the starting manganese(iii) porphyrin complex with a half-
life of 450 s (data not shown).
[16] Into a reaction solution of [Mn(TF4TMAP)]5 (7 Â 10À2 mm) and CBZ
(5 Â 10À1 mm) in 0.1m pH 10.5 borate buffer (0.25 mL, 85% 18O-
enriched), H2O2 (1mm) was added in five portions (0.2mm each) at
30 min intervals, at 08C. The conversion of CBZ was 80% and the
yield of CBZ-10,11-oxide was 40% based on H2O2 added. Detailed
experimentalprocedures for the determination of the epoxide yiedl
and the percentage of 18O in the epoxide product are described in the
ExperimentalSection.
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[18] All the experimental procedures were as described in [16] except that
18O-labeled H218O2 was used as an oxidant.
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[20] cis-Stilbene has been often used as a mechanistic probe in studies of
À
the mechanism of O O bond cleavage of hydroperoxides by metal
complexes: a) G.-X. He, T. C. Bruice, J. Am. Chem. Soc. 1991, 113,
2747 2753; b) A. J. Castellino, T. C. Bruice, J. Am. Chem. Soc. 1988,
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[11] The stability of the intermediate 1 depends on the pH values of the
reaction solution, in which 1 is relatively stable at high pH (>pH 10);
as the pH of the reaction solution decreases, either 1 decays fast
(pH ꢀ 9) or the formation of 1 is not detectable (pH < 8). The pH
dependence of the stability of an oxomanganese(v) porphyrin complex
[21] The pH-dependent activity of manganese and iron microperoxidases 8
has been observed in the catalytic oxidation of organic substrates by
H2O2: J.-L. Primus, M. G. Boersma, D. Mandon, S. Boeren, C. Veeger,
R. Weiss, I. M. C. M. Rietjens, J. Biol. Inorg. Chem. 1999, 4, 274 283.
[22] We do not know why homolysis takes place at low pH and heterolysis
[(TM-2-PyP)MnV O] has been reported previously: see ref. [7e].
À
[12] a) P. A. MacFaul, D. D. M. Wayner, K. U. Ingold, Acc. Chem. Res.
1998, 31, 159 162; b) P. A. MacFaul, K. U. Ingold, D. D. M. Wayner,
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predominates at high pH in manganese(iii) porphyrin-mediated O O
bond cleavage of H2O2 and why the pH-dependent patterns of
À
HO OH bond cleavage by manganese(iii) and iron(iii) porphyrin
complexes are mutual opposites. More detailed mechanistic studies
À
are needed to elucidate the effect of pH on the O O bond cleavage
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mechanism in manganese and iron porphyrin systems.
[23] H. Saltzman, J. G. Sharefkin, Organic Syntheses, Collection Vol. V,
Wiley, New York, 1973, p. 658.
Received: October 31, 2001 [F3646]
Chem. Eur. J. 2002, 8, No. 9
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