ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2006, Vol. 32, No. 9, pp. 686–691. © Pleiades Publishing, Inc., 2006.
Original Russian Text © A.S. Burlov, A.I. Uraev, K.A. Lysenko, G.G. Chigarenko, A.G. Ponomarenko, P.V. Matuev, S.A. Nikolaevskii, E.D. Garnovskaya, G.S. Borodkin,
A.D. Garnovskii, 2006, published in Koordinatsionnaya Khimiya, 2006, Vol. 32, No. 9, pp. 714–719.
Complex compounds of azo ligands are always in
the focus of researchers’ attention [1–4]. Azo ligand
chelate complexes were used to establish and develop
important theoretical concepts about chelate isomeriza-
tion (realization of metal cycles with different members
in the molecule of a complex) [3–5], about stabilization
as a result of complexation of different tautomeric
forms of the ligand systems , and isolation of
-isomers [6, 7].
Metal complexes of azo compounds have wide prac-
tical application, including the production of dyes and
pigments [1, 8, 9].
In this work, the most poorly studied atomatic azo
chelates with the MN
coordination core are synthe-
sized and their structures are determined by X-ray dif-
fraction. Their tribochemical activity (the possibility of
using as lubricant addivites) is shown. Azo chelates are
obtained by the following scheme:
N R + MAc
Synthesis of ligands.
The starting compounds
were prepared according to the known procedures [1,
10], i.e., by diazotization of
niline and coupling with N-phenyl-2-naphthylamine.
Synthesis of complex compounds II.
To a solution
of 4-(2'-N-phenylaminonaphthylazo)toluene (0.67 g,
2 mmol) in 50 ml methanol, a solution of Cu acetate
monohydrate (0.2 g, 1 mmol) in 20 ml methanol was
, M = Cu) or to a solution of 4-(2'-N-pheny-
laminonaphthylazo)chlorobenzene (0.72 g, 2 mmol) in
50 ml methanol, a solution of Pd acetate (0.22 g,
1 mmol) in 10 ml acetone was added (
, M = Pd). The
reaction mixture was boiled on a water bath for 1 h and
cooled. The obtained precipitates of the complexes
were ﬁltered off, washed twice with 5-ml portions of
The complexes were recrystallized and their crystals
for X-ray diffraction analysis were grown from methyl-
ene chloride–methanol mixture (1 : 2).
. Dark brown crystals,
Anal. calcd. (%): ë 75.12; ç 4.95; N 11.35; Cu 8.55.
Found (%): ë 75.02; ç 4.93; N 11.41; Cu 8.63.
Novel Tribochemically Active Metal Chelates
of Aromatic Azo Ligands
A. S. Burlov
, A. I. Uraev
, K. A. Lysenko
, G. G. Chigarenko
, A. G. Ponomarenko
, P. V. Matuev
S. A. Nikolaevskii
, E. D. Garnovskaya
, G. S. Borodkin
, and A. D. Garnovskii
Institute of Physical and Organic Chemistry, Rostov State University, pr. Stachki 194/3, Rostov-on-Don, 344104 Russia
Nesmayanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Invek RD Ltd., Rostov-on-Don, Russia
Received June 3, 2005
—Novel Cu(II) and Pd(II) complexes with
-phenylaminoazo compounds were synthesized and stud-
ied by X-ray diffraction. Distorted tetrahedral chelate complex of Cu contains two six-membered CuN
cycles. The complexes under study can be used as industrial lubricant additives.