B. D. Berezin

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.

Synthesis and use of ecologically pure metal-containing dyes based on chlorophyll derivatives

The problem of the use of a natural pigment, chlorophyll, as ecologically pure dye for textile fibers is discussed. The physicochemical principles of the synthesis of metalocontaining compounds based on chlorophyll derivatives used for development of chlorophyll and porphyrin dyes of new generation, which are more ecologically safe than the arene-based dyes.

Kinetics of Metal Exchange Between Cadmium Mesoporphyrin and Zinc and Cobalt Salts in Organic Solvents

Transmetalation of Cd-mesoporphyrin with cobalt chloride in acetonitrile and with zinc chloride in dimethyl sulfoxide was performed and studied by spectrophotometric method.

Manganese Complexes with Octaphenyltetraazaporphine: Acid–Base Interactions and Kinetic Stability in Proton-Donor Solvents

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 pK1 = 0.29 ± 0.01 and pK2 = –0.62 ± 0.08 for (chlorine)manganese(III)octaphenyltetraazaporphine ((Cl)MnOPTAP); pK1 = 0.99 ± 0.02 and pK2 = – 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.

Reactions of Chelates with Macrocyclic Ligands. Complexation between Tetraphenylporphine and Cu(II) Complexes with α-Amino Acids

The reactions of tetraphenylporphine (H2TPP) with copper(II) chelates in DMSO were studied. α-Amino acids (glycine, α-alanine, valine, leucine, tyrosine, and glutamine) were used as chelating ligands. The study of the reaction kinetics showed that Cu(II) chelates with alanine and the other amino acids are less reactive in these reactions than acetylacetonates, α-nitroso-β-naphtholates, and hydroxyquinolates. The exception is a Cu(II) complex with tyrosine. The relationship between the structure of the above chelates and the rate of their reactions with porphyrin was determined.

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.

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.

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.