1070-4272/05/7806-0897 + 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 6, 2005, pp. 897!902. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 6, 2005,
Original Russian Text Copyright + 2005 by Frolov, Bolotin, Panyshkin.
AND CORROSION PROTECTION OF METALS
Electrochemical Synthesis of Complex Compounds
of Transition Elements with Carboxyl-
and Carbonyl-containing Ligands
V. Yu. Frolov, S. N. Bolotin, and V. T. Panyshkin
Kuban State University, Krasnodar, Russia
Received February 25, 2004
Abstract-Complex compounds of d- and f-elements with carboxyl- and carbonyl-containing ligands were
synthesized by the electrochemical method. The influence exerted by a number of factors on the process
course was studied. The dependence of the electrosynthesis parameters on the composition of the forming
compounds was established. The composition of these compounds was determined. A new method for anodic
synthesis of these compounds was developed.
The electrochemical method simplifies synthesis
of known compounds  and makes it possible to
synthesize compounds that cannot be obtained other-
wise . Moreover, the advantage of the anodic syn-
thesis is in that the process can be controlled and per-
formed in mild conditions with a high yield and purity
of the final products .
Despite that the electrosynthesis is one of the oldest
methods for synthesis of coordination compounds ,
the analysis of the anodic synthesis methods in
[137, 9313] shows that many problems concerning
the theory and practical application of the method
have not been studied.
Transition-metal carboxylates of composition
(M = Cr; R = C
; n =3;M=
Mn, Fe, or Ni; R = CH
n = 2) have been prepared  by electrochemical
oxidation of the corresponding metals in solutions of
carboxylic acids RCOOH in acetonitrile. In ,
monocarboxylic acids containing one to four atoms
in the carbon chain were successfully used to syn-
salts. Oxalate complexes of iron
and copper were synthesized by the electrochemical
method in . On the whole, publications devoted to
carboxylate complexes are scarce and analyze a rather
small number of the ligands.
The goal of this study was to develop new original
methods that would enable application of the electro-
chemical synthesis in a wider range and to a larger
number of objects and make it possible to perform di-
rected syntheses in which the composition of the form-
ing products is controlled by varying the process con-
ditions (ligand concentration, temperature, solvent,
and electrode potential), and also to compare the prop-
erties of compounds synthesized by electrochemical
methods with those produced by chemical methods.
Acetylacetonates of rare-earth elements (REE) were
synthesized to confirm the suggestion that substances
exhibiting a tendency toward sublimation, which could
not be synthesized previously by other methods [19,
20], can be obtained by electrochemical synthesis.
The installation for anodic synthesis (Fig. 1) com-
prised a three-electrode cell, PI-50-1 potentiostat,
Fig. 1. Schematic of a three-electrode cell for electrochem-
ical anodic synthesis (1) Thermostating jacket, (2) stirrer,
(3) outlet, (4) inlet, (5) separator, (6) working electrode,
(7) auxiliary electrode, and (8) reference electrode.