Structure of zinc-5,15-di(o-methoxyphenyl)octaalkylporphyrines and their reaction with organic peroxides in the presence of pyridine |
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Authors: | S V Zaitseva O R Simonova and O I Koifman |
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Institution: | (1) Inst. Anorganische und Analytische Chemie, Universit?t Mainz, Staudingerweg 9, 55099 Mainz, Germany;(2) MPI f?r Bioanorganische, Chemie, Stiftstr. 34-36, 45470 M?lheim, Germany;(3) Inst. Physik, Universit?t L?beck, Ratzeburger Allee 160, 23538 L?beck, Germany |
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Abstract: | By combined spectral and calculation methods the structure of zinc 5,15-di(o-methoxyphenyl)-2,8,12,18 3,7,13,17-octaalkylporphyrinates (I, II) and their properties in the reaction with organic peroxides with addition of different amounts of pyridine were studied.
The reaction of zinc porphyrinates with peroxides in the presence of pyridine leads to destruction of the complex chromophore.
Kinetic parameters of the investigated reaction (effective k
ef and true k
V rate constants) are obtained. The presence of base in the reaction medium is found to lead to a change in the structure of
the zinc porphyrinates and affects the rate of oxidation. By quantum-chemical method PM3 the geometry of the reagents was
calculated and the deformation distortions of the reactants molecules and intermediates in the course of the oxidation reaction
was demonstrated. The influence of electronic effects of substituents and the degree of deformation of the zinc porphyrinate
macrocycle on their redox properties is revealed. |
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Keywords: | |
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