O. V. Mal’tseva

Copper(II), cobalt(II), cobalt(III), and tin(IV) 5,10,15,20-tetraphenyl tetrabenzoporphyrinates: Synthesis and properties

The complexation reactions of 5,10,15,20-tetraphenyl tetrabenzoporphyrin and the metal exchange reactions of its cadmium(II) complex with copper(II), cobalt(II), and tin(II) acetates and chlorides in a chloroform–methanol mixture and dimethylformamide were studied spectrophotometrically. Corresponding copper(II), cobalt(II), cobalt(II), and tin(IV) porphyrinates were synthesized and identified.

Synthesis and spectral properties of meso-substituted Ni2+ octaalkylporphyrinates

Nickel(II) 3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinate and its 5,15-diaza, -diphenyl, and -di(4-bromophenyl) derivatives have been synthesized by the reaction of nickel(II) chloride with corresponding tetrapyrrole ligands in dimethylformamide.

Spectral and complex-forming properties of β-bromo-substituted porphyrins in N,N-dimethylformamide

Contributions of structural and electronic effects to the reactivity and chromophore properties of tetrapyrrole macrocycles modified by bromine atoms were revealed on the basis of the kinetic data on the complex formation of 2-bromo-5,10,15,20-tetraphenylporphyrin, 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin, and 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin with zinc(II) and copper(II) acetates in N,N-dimethylformamide, and also by measuring spectral characteristics of porphyrin ligands and zinc and copper porphyrinates.

Synthesis and Spectral Properties of Ni(II), Pd(II), Pt(II), and Pt(IV) Tetraphenyltetrabenzoporphyrinates

Complexation reactions of 5,10,15,20-tetraphenyltetrabenzoporphyrin and transmetallation of its cadmium complex with nickel(II) acetate, Ni(II), Pd(II), and Pt(II) chlorides in dimethylformamide and phenol have been studied. The corresponding Ni(II), Pd(II), and Pt(II) porphyrinates have been synthesized. PtIVBr2 porphyrinate has been obtained by the treatment of Pt(II) 5,10,15,20-tetraphenyltetrabenzoporphyrinate with bromine in chloroform. The obtained compounds have been characterized by elemental analysis, electronic absorption and 1H NMR spectroscopy and mass spectrometry.

Synthesis and spectral properties of β-bromo-substituted nickel(II) tetraphenylporphyrins

Bromination of (5,10,15,20-tetraphenylporphyrinato)nickel(II) with N-bromosuccinimide in chloroform and chloroform–dimethylformamide mixture and complexation of 2-bromo-5,10,15,20-tetraphenylporphyrin and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with nickel(II) acetate in dimethylformamide have been studied. The resulting nickel(II) complexes with mono-, tetra-, and octabromo-5,10,15,20-tetraphenylporphyrins have been identified by electronic absorption, IR, 1H NMR, and mass spectra.

β-Bromo-substituted palladium(II) tetraphenylporphyrins. Synthesis and spectral properties

Bromination of (5,10,15,20-tetraphenylporphyrinato)palladium(II) and [5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]palladium(II) with N-bromosuccinimide in chloroform–dimethylformamide and chloroform afforded mono-, tetra-, and octabromo derivatives substituted at the pyrrole rings. The products were identified by electronic absorption, 1H NMR, and mass spectra and elemental analyses.

Synthesis and properties of manganese complexes of meso-tetraphenyltetrabenzoporphyrin

The coordination of meso-tetraphenyltetrabenzoporphyrin and metal exchange of its Cd(II) complex with manganese(II) chloride and acetate in DMF and a chloroform–methanol mixture have been studied by spectrophotometry. The Mn(III) chloride and acetate acido complexes formed in these reactions have been isolated and characterized. The dissolution of the synthesized complexes in DMF in the presence of solid KOH gives Mn(II) meso-tetraphenyltetrabenzoporphyrinate.

Metal-exchange reaction between cadmium tetraphenylporphyrinates and copper(II) in dimethylformamide

The metal-exchange reaction of cadmium 5,10,15,20-tetraphenylporphyrinate (CdTPP) and cadmium 2-bromo-5,10,15,20-tetraphenylporphyrinate (CdTPPBr) with copper acetate (Cu(OAc)2) in dimethylformamide was studied spectrophotometrically. The kinetic parameters of the metal-exchange reaction were determined. A possible stoichiometric reaction mechanism was proposed.

Synthesis and properties of dimeric octaalkylporphyrins with a polyether linker

Octaalkylporphyrin dimers with a polyether linker were synthesized, and their physicochemical properties were studied. Specific response of the tetrapyrrole chromophore to complexation with potassium cation at the polyether moiety was examined.

Effect of the Type of Molecular Nonplanar Structure on the Chemical Reactivity of NH Bonds in the Coordination Center of Porphyrin Molecule

Effect of out-of-plane screwing of the porphyrin macrocycle (H2P) by means of tetra-meso-substitution and intracyclic N-substitution on the state of NH bonds in the molecule is explored. By applying 1H NMR, kinetic and quantum-chemical criteria of evaluation of the macrocycle NH-reactivity is found that such type of H2P screwing does not increase reactivity of the NH bonds. It is shown that increased chemical NH activity is observed only in the porphyrins undergoing at a significant conformational screwing possess the polarization of the molecular π-system.