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(β‐Octafluoro‐ meso ‐tetraarylporphyrin)manganese Complexes: Synthesis, Characterization and Catalytic Behaviour in Monooxygenation Reactions
Author(s) -
Porhiel Emmanuel,
Bondon Arnaud,
Leroy Jacques
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200005)2000:5<1097::aid-ejic1097>3.0.co;2-2
Subject(s) - chemistry , manganese , catalysis , hydrogen peroxide , hydroxylation , porphyrin , cyclohexane , aryl , chlorine , peroxide , redox , medicinal chemistry , photochemistry , inorganic chemistry , polymer chemistry , organic chemistry , alkyl , enzyme
The synthesis and characterization of manganese complexes of β‐octafluoro‐ meso ‐tetraarylporphyrins are reported. The presence of the electron‐withdrawing β‐fluorine atoms induces a very large shift of the redox potential for the oxidation of the manganese(II) derivatives. With the meso ‐aryl group bearing two ortho ‐chlorine atoms (2,6‐dichlorophenyl) or five fluorine atoms (pentafluorophenyl), metal complexation leads to the isolation of pure manganese(II) compounds. The stability and catalytic activity of these new derivatives have been studied using hydrogen peroxide and iodosylbenzene as oxidants, and standard substrates for epoxidation and hydroxylation reactions. The results are compared to those obtained with the β‐hydrogenated analogs under the same conditions. In the case of hydrogen peroxide, the high level of porphyrin degradation prevents efficient catalytic activity. With iodosylbenzene as oxidant, both stability and epoxidation are similar to those of the β‐hydrogenated porphyrins, however, a substantial improvement in the efficiency of the hydroxylation of cyclohexane is observed with up to 33 turnovers with (perfluorotetraphenylporphyrin)manganese(II).