Manganese Complexes with Octaphenyltetraazaporphine: Acid–Base Interactions and Kinetic Stability in Proton-Donor Solvents |
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| Authors: | Klyueva M E Stuzhin P A Berezin B D |
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| Institution: | (1) Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045, Russia;(2) Ivanovo State University of Chemical Technology, Ivanovo, Russia |
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| Abstract: | Complexes of manganese(III) and manganese(V) with octaphenyltetraazaporphine (H2OPTAP) were synthesized. Acid–base interactions of these complexes in the CH2Cl2–CF3COOH system and kinetics of their dissociation in concentrated sulfuric acid, as well as kinetics of octaphenyltetraazaporphine destruction in sulfuric acid solutions were studied by spectrophotometric methods. Acid–base interactions in CH2Cl2–CF3COOH were shown to involve two macrocyclic meso-nitrogen atoms in succession. Concentration stability constants of the acid forms obtained pK
1 = 0.29 ± 0.01 and pK
2 = –0.62 ± 0.08 for (chlorine)manganese(III)octaphenyltetraazaporphine ((Cl)MnOPTAP); pK
1 = 0.99 ± 0.02 and pK
2 = – 0.70 ± 0.03 for (nitrido)manganese(V)octaphenyltetraazaporphine ((N)MnOPTAP). The rate of dissociation of the complexes in 94–98% H2SO4 does not depend on the acid concentration. The manganese(V) complex is three times as stable as the manganese(III) complex. |
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