S. V. Zvezdina

Metal exchange reactions between cadmium protoporphyrin and cobalt and zinc chlorides in acetonitrile and dimethyl sulfoxide

Metal exchange between cadmium protoporphyrin CdPP and zinc and cobalt chlorides in dimethyl sulfoxide (DMSO) and acetonitrile (AN) was studied by spectrophotometry. Comparative analysis of the data on metal exchange between CdPP and ZnCl2 in DMSO and between CdPP and CoCl2 in AN was performed. The possible exchange mechanisms were considered. The results were compared with the data on cadmium mesoporphyrin exchange with zinc and cobalt.

Double metal-ligand exchange in solvate complex-metal porphyrin systems

The kinetics and mechanism of one of the most complicated chemical reactions of coordination compounds, where two different porphyrin complexes exchange central metal ions and the corresponding ligands, were considered using a number of metal porphyrins as substrates.

Metal exchange reaction of cadmium 5-monoaza-2,3,7,8,12,13,17,18-octamethylporphyrinate with zinc(II) and copper(II) chlorides in dimethyl sulfoxide

The metal exchange reactions of cadmium 5-monoaza-2,3,7,8,12,13,17,18-octamethylporphyrinate with CuCl2 and ZnCl2 in dimethyl sulfoxide (DMSO) were studied by spectrophotometry. The kinetic and energy parameters of the metal exchange reaction were determined. The possible stoichiometric mechanism of the metal exchange reaction was proposed. A comparative analysis of the reaction rate constants obtained for the metal exchange and for the complex formation of 5-monoaza-2,3,7,8,12,13,17,18-octamethylporphyrin with the same salts in DMSO was performed.

Cadmium(II) for zinc(II) exchange reactions in deutero- and hematoporphyrin complexes in dimethyl sulfoxide

The metal-exchange reaction between Cd-deuteroporphyrin or Cd-ematoporphyrin and ZnCl2 in dimethyl sulfoxide (DMSO) was studied spectrophotometrically. The order and activation parameters of the reaction of Cd2+ replacement by zinc ions were calculated. A mechanism of this reaction is suggested. The results are compared with the available data on metal-exchange reactions between Cd-mesoporphyrin and Cdprotoporphyrin and ZnCl2 in DMSO.

Preparation and spectral properties of β-bromo-substituted Mn(III) tetraphenylporphyrinates

Interaction of 5,10,15,20-tetraphenylporphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with manganese(II) chloride in dimethylformamide has been studied by means of spectrophotometry. The corresponding chloride acido complexes of manganese(III) has been so prepared and identified. The complexes could be reduced into manganese(II) tetraphenylporphyrinates in the presence of potassium hydroxide in dimethylformamide.

Transmetalation of (octaphenyltetraazaporphyrinato)magnesium(II) with manganese(II) chloride in dimethylformamide

The reaction of (octaphenyltetraazaporphyrinato)magnesium(II) with manganese(II) chloride in dimethylformamide gave (chloro)(octaphenyltetraazaporphyrinato)manganese(III). Reactions of the latter with nitrogen-containing bases were studied. The kinetic parameters of the transmetalation of (octaphenyltetraazaporphyrinato) magnesium(II) with MnCl2 in dimethylformamide at 323, 333, and 343 K were determined, and a probable reaction mechanism was proposed.

Natural dyes based on chlorophyll and protoporphyrin derivatives

The utility of natural dyes (chlorophyll, protoporphyrin, and their derivatives) as ecologically pure new-generation dyes that are safer than common synthetic arene-based dyes is discussed. New dyes were obtained from chlorophyll and protoporphyrin derivatives such as pheophorbide (a+b), chlorin e6, 6-N-(2-aminoethylamido)chlorin e6 dimethyl ester, and 6-N-(2-aminoethylamido)deuteroporphyrin methyl ester and tested in coloration of wool, cotton, and acetate fibers.

Kinetics of the metal-exchange reaction of deuteroporphyrin and gematoporphyrin cadmium complexes with cobalt chloride in acetonitrile

The metal-exchange reaction of cadmium deuteroporphyrin (CdDP) and cadmium gematoporphyrin (CdGP) with cobalt chloride in acetonitrile is studied spectrophotometrically. The stoichiometry of the metal-exchange reaction is determined. The results are compared with the exchange reaction of cadmium mesoporphyrin and cadmium protoporphyrin with cobalt acetate in acetonitrile. Substituents in the 2,4-positions of cadmium complexes of protoporphyrins are shown to influence the rate of the metal-exchange reaction. The increasing order of the rates of the metal-exchange reaction between protoporphyrins and cobalt chloride in acetonitrile is established.

On the mechanism of the metal exchange in natural cadmium porphyrins

The kinetics of the exchange of the Cd2+ ions in the complexes with the natural protogroup porphyrins (protoporphyrin, mesoporphyrin, deuteroporphyrin, and hematoporphyrin) for the Zn2+ ions is studied. The stoichiometric ratios of components in the reaction of cadmium exchange for zinc in acetonitrile and DMSO are established. The results obtained are compared with the previously published data for the reaction withthe Co2+ ions. The activation mechanism of the metal exchange reaction is considered, depending on the effect of the nature of substituents in porphyrin, d-metal ions, and a solvent.

Metal-exchange reaction of Mg-octaphenyltetraazaporphyrin with Co(II)

The metal-exchange reaction of Mg(II)-octaphenyltetraazaporphyrin with CoCl2 leading to formation of Co(II)-octaphenyltetraazaporphyrin was studied by the method of UV-vis spectroscopy. The kinetic parameters of the metal-exchange reaction were determined.