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Abstract
The mechanism of peracetic acid interaction with Mn(III) complexes of tetra-R-tetra- tert-butyl-tetraazaporphines (RTAPMnCl, R=H, Br, PhSO 2, NO 2) in acetonotrile/acetic acid solutions has been studied. Analysis of the kinetic data of trans-stilbene epoxidation, naphthalene hydroxylation, 1,1-diphenyl-2-picrylhydrazine (DPPH), and tetra-4- tert-butyl-phthalocyanine zinc (PcZn) one-electron oxidations revealed the reversible formation of a two-center molecular “catalyst–oxidant” complex ligated with a molecule of acetic acid { A =[ RTAPMn(AcOOH)(AcOH)](X)}. The subsequent irreversible transformation of A with rate constant k 2 leads to the formation of two high-valent oxometallo species, supposedly [RTAPMn(V)(O)(AcOH)](X) and [ +RTAPMn(IV)(O)(AcOH)](X), which are in equilibrium and show distinct oxidation abilities towards olefin and naphthalene. The Hammett-type dependencies of k 2 and of the rate constant of A formation ( k 1) have been analyzed and compared with those ones determined earlier for Mn(III) meso-tetra(2,6-dichloro-4-R-phenyl)porphyrins (RTDCPPMnCl). The enhanced sensibility of the acceptor properties of Mn ion to electronegative substitution in tetraazaporphine macrocycle is considered to be a reason of the highest catalytic oxidative activity of Mn-tetra-nitro-tetra- tert-butyltetraazaporphine within studied Mn porphinoids.
Published Version
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