5,15-bis(4′-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphin axial complexes of rhenium: Synthesis and reactions in protic solvents


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The spectral (UV–Vis, IR, and NMR 1H) properties and the state of oxorhenium(V) complexes with 5,15-bis(4′-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphin H2P (O=Re(X)P) in protic solvents have been studied depending on the axial trans-ligand X (X = Cl, OPh, or OH). The O=Re(Cl)P, O=Re(OPh)P, and O=Re(OH)P in AcOH and CF3COOH are subjected to reaction of substitution their axial ligands with solvent molecules or anions, while remaining stable to the dissociation of M–N bonds and to oxidation both to the macrocyclic ligand and to the central metal cation. Quantitative parameters of the coordination of molecular oxygen by O=Re(Cl)P in 17.4–18.2 M H2SO4 to form O=Re(O2)P+ · Cl have been obtained, these parameters being independent of the initial H2SO4 concentration. The character of peripheral functional substituents in H2P has been shown to be responsible for the stability of the studied oxo complexes to chemical oxidation in aerated acids.

Sobre autores

E. Tyulyaeva

G.A. Krestov Institute of Solution Chemistry

Email: tnl@isc-ras.ru
Rússia, Ivanovo, 153045

N. Bichan

G.A. Krestov Institute of Solution Chemistry

Email: tnl@isc-ras.ru
Rússia, Ivanovo, 153045

T. Lomova

G.A. Krestov Institute of Solution Chemistry

Autor responsável pela correspondência
Email: tnl@isc-ras.ru
Rússia, Ivanovo, 153045

A. Semeikin

Ivanovo State University of Chemical Technology

Email: tnl@isc-ras.ru
Rússia, Ivanovo, 153000

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