ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 11, pp. 1910 !1913. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + V.M. Misin, N.N. Glagolev, M.V. Misin, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 11, pp. 1886 !1889.
AND POLYMERIC MATERIALS
Structure and Properties
of Polymeric Ethyne!Hexacarbonyldicobalt F Complexes
V. M. Misin, N. N. Glagolev, and M. V. Misin
Emanuel’ Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
Received March 16, 2007
Abstract-A polymeric ethyne3hexacarbonyldicobalt p complex was prepared by the reaction of poly-p-di-
ethynylbenzene with Co
. The conformations in which the polymer chains can exist and the conforma-
tions in which the 3C=CH and 3Ph3 groups can form p complexes with Co
were revealed by analysis
of Stuart3Briegleb molecular models. The IR spectra of the polymeric complexes were analyzed, and their
thermal degradation in air was examined.
Interest in polymers containing metal atoms p-co-
ordinated to organic macromolecules is due to the
possibility of preparing catalytically active systems
based on such polymers. Catalytic systems in which
a transition metal is p-coordinated to a polymeric sup-
port acting as a macroligand are well known . Of
particular interest are p complexes with polyconju-
gated polymers, because of their specific physico-
chemical, electrophysical, and catalytic properties.
In particular, some of these complexes are organo-
metallic ferromagnetics, i.e., materials absorbing or
scattering electromagnetic fields. Sergeev et al. 
prepared p-arene3tricarbonylmetal complexes derived
from carbonyls of molybdenum, chromium, vanadi-
um, and various polyphenylenes. At the same time,
numerous p-acetylene3hexacarbonyldicobalt com-
plexes with various mono- and disubstituted acetyl-
enes as ligands are known .
Therefore, it seemed interesting to synthesize
p complexes of metal carbonyls with polysubstituted
polymers containing ethynyl groups 3C=CH.
Previously  we described preparation and molec-
ular structure of poly-p-diethynylbenzene (PDEB), a
polyconjugated polyene polymer containing ethynyl
groups in pendant chains, 3[HC=C(p-C
. The polymer was prepared by selective polymeri-
zation of p-diethynylbenzene HC=C3( p-C
via one of the 3C=CH groups in the presence of an
anionic initiator. The use of such polymers opens
prospects for preparing diverse complexes whose
structure will be preset by both the polymeric chain
and the complexing metal fragment. By properly
choosing the type and amount of the complexing
metal species, it may be possible to prepare in a poly-
meric matrix both small organometallic fragments and
relatively lengthy metal clusters.
This study deals with the synthesis of p-acetylene
complexes with a metal carbonyl, based on PDEB.
As metal carbonyl we took octacarbonyldicobalt,
The starting PDEB is an X-ray amorphous brown
polymer soluble in aromatic and polar solvents. To
prepare polymeric complexes, we used polymers with
a number-average molecular weight of 3500, contain-
ing 0.62 ethynyl group per monomeric unit of the
Ethyne!hexacarbonyldicobalt F complex with
PDEB (PDEBC). A reactor preliminarily purged with
argon was charged with 0.3 g of PDEB in 30 ml of
benzene, and a solution of 0.19 g of Co
in 6 ml
of benzene was added dropwise. The reaction was
performed at room temperature until the CO evolution
ceased. The presence of unchanged Co
monitored by TLC on Silufol, eluent hexane. After
3 h, the solution was filtered and the product was
precipitated into hexane at the solvent : precipitant
ratio of 1 : 10. Yield of PDEBC 0.31 g (68%).
The IR spectra were recorded on a UR-20 spectro-
photometer from KBr pellets (1%) or from 5% ben-
zene solutions. The ESR spectra were taken on an