T. V. Magdesieva

Electrocatalytic dehalogenation of α-bromoketones in the presence of Cp2TiCl2

Processes of direct and electrocatalytic (in the presence of electrochemically reduced Cp2TiCl2) reduction of three α-bromoketones containing the C(sp3)-Br or C(sp2)-Br bond, viz., 2-bromo-and 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-ones and α-bromo-acetophenone, were studied by cyclic voltammetry and preparative electrolysis. In all cases, the dissociative electron transfer proceeds via the concerted mechanism. Preparative electrolysis of these α-bromoketones in the presence of Cp2TiCl2 affords the reductive debromination products in 40–80% yield at low cathodic potentials (−0.85 V vs. Ag/AgCl/KCl). In the case of 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-one in the potentiostatic regime, only one bromine atom can be eliminated selectively.

Synthesis and characteristics of novel pentanuclear complexes [(OC)3Mn(η1,η5-C5H4)Fe(CO)2(η1,η5-C5H4CO2)]2M(η5-C5H5)2 (M=Ti, Zr)

The reaction of Cp2MCl2 complexes (M=Ti and Zr) with 2 equiv. of (OC)3Mn(η1,η5-C5H4)Fe(CO)2(η5-C5H4COONa) results in the formation of the pentanuclear complexes (OC)3Mn(η1,η5-C5H4)Fe(CO)2(η5-C5H4CO2)]2M(η5-C5H5)2, which are characterized by IR and1H NMR spectroscopy and cyclic voltammetry.

Copper(i) complexes with polymeric 2,2′-biquinoline-containing ligands as electrocatalysts for selective oxidation of the secondary hydroxy group in 3,24-dihydroxy-5β-cholane with oxygen

Indirect electrocatalytic selective oxidation of the secondary hydroxy group in 3,24-dihydroxy-5β-cholane was performed using atmospheric oxygen in the presence of copper(I) complex with a polymeric 2,2′-biquinoline-containing ligand as catalyst. The reaction was characterized by a high yield (85%), 100% selectivity, and mild conditions, the CuII/CuI redox potential being −0.55 V relative to Ag/AgCl/KCl.

Metallation of fullerenes: electrochemical synthesis and voltammetric study of heterometallic C60 and C70 complexes

Electrochemical synthesis and voltammetric study of new heterotrimetallic exohedral derivatives of [60]- and [70]fullerenes containing palladium and manganese atoms were carried out. The MO involved in redox transitions were determined by the semiempirical quantum-chemical calculations and by the comparison of the potentials for the redox transitions of the heterotrimetallic complexes and their fullerene and metal-containing fragments.

Electrochemical arylation of cobalt and nickel chelates with diphenyliodonium salts

Electrochemical arylation of cobalt chelates with diphenyliodonium salts occurs at low cathodic potentials (viz., potential of the first reduction wave of the diphenyliodonium salt) and affords the phenyl derivatives of CoIII chelates containing the σ-Co—C(sp2) bond. Nickel complexes should be arylated at higher cathodic potentials because it is necessary to generate paramagnetic NiI complexes.