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KNIZHNIKOV et al.
Cyclopentadienyl(methyldiphenylphosphine)-
cobalt diiodide (I). a. A solution of 0.127 g of
iodine in 25 ml of benzene was added to a solution of
0.24 g of cyclopentadienyl(tetraphenylbutadiene)-
cobalt and 0.1 g of methyldiphenylphosphine in 50 ml
of benzene. The reaction mixture was stirred for 2 h
and filtered. The resulting solution was reduced to
10 ml in a vacuum and treated with 75 ml of hexane.
A precipitate formed and was separated, washed with
hexane, and dried in a vacuum. Reprecipitation from
benzene gave 0.24 g (83%) of compound I, mp 153
155 C. Found, %: C 37.56; H 3.30; I 43.72. C18H18
CoI2P. Calculated, %: C 37.40; H 3.14; I 43.91.
L = Ph3P (II), Ph2PMe (III).
Compounds II V are colored solid substances
soluble in polar organic solvents. The structure of the
1
compounds was proved by the H NMR and IR spec-
tra (Table 2) and by the elemental analyses.
b. To a suspension of 0.378 g of cyclopentadienyl-
cobalt diiodide in 75 ml of benzene, 0.2 g of diphenyl-
methylphosphine was added. The reaction mixture
was stirred for 8 h and filtered. The reaction product
was isolated and purified as in procedure a. We ob-
tained 0.44 g (76%) of compound I, mp 154 155 C.
Bis(methyldiphenylphosphine)cyclopentadienyl-
iodocobalt iodide (III). To a solution of 0.289 g of
cyclopentadienyl(methyldiphenylphosphine)cobalt
diiodide in 50 ml of methylene chloride, 0.1 g of
methyldiphenylphosphine was added. The reaction
mixture was stirred for 10 h and filtered. The resulting
solution was treated with 40 ml of hexane and reduced
to 50 ml in a vacuum. A precipitate formed and was
separated, sequentially washed with ether and pentane,
and dried in a vacuum. Reprecipitation from me-
thylene chloride gave 0.31 g (80%) of compound III,
mp 98 100 C. Found, %: C 48.01; H 4.28; I 32.40.
C31H31CoI2P2. Calculated, %: C 47.84; H 4.01;
I 32.61.
L = Ph3P (IV), Ph2PMe (V).
EXPERIMENTAL
The IR spectra were recorded in KBr pellets on a
1
Protege-460 spectrophotometer. The H NMR spectra
were recorded on a Tesla BS-567A spectrometer for
solutions in (CD3)2CO against TMS. The mass spec-
trum of cyclopentadienyl(methyldiphenylmethylphos-
phine)cobalt diiodide was obtained on an MX-1320
instrument, ionizing energy 35 eV. The starting
cyclopentadienyl(tetraphenylbutadiene)cobalt
cyclopentadienyl(triphenylphosphine)cobalt diiodides
were synthesized by published procedures [1].
and
Similarly, from 0.32 g of cyclopentadienyl(tri-
phenylphosphine)cobalt diiodide and 0.1 g of methyl-
diphenylphosphine we obtained 0.32 g (76%) of
compound II, mp 47 49 C. Found, %: C 51.68; H
4.22; I 29.96. C36H33CoI2P2. Calculated, %: C 51.45;
H 3.96; I 30.20.
All operations were carried out under argon using
anhydrous organic solvents.
1
Table 2. H NMR spectra ( , ppm) of compounds II V
Comp.
no.
C5H5
C6H5
CH3
Bis(methyldiphenylphosphine)cyclopentadienyl-
iodocobalt tetraphenylborate (V). To a solution of
0.389 g of compound III in 75 ml of methylene chlo-
ride, 0.171 g of sodium tetraphenylborate was added.
The reaction mixture was stirred for 12 h and filtered.
The resulting solution was concentrated in a vacuum
until crystallization began and treated with hexane.
The precipitate was separated, washed with ether and
pentane, and dried in a vacuum. Reprecipitation from
II
5.23 s (5H) 7.4 8.2 m (25H)
5.78 s (5H) 7.3 8.1 m (20H)
2.50 d (3H)
1.8 d (3H),
1.9 d (3H)
2.50 d (3H)
III
IV
V
5.21 s (5H) 6.7 7.1 m (12H)
7.3 8.0 m (33H)
5.67 s (5H) 6.7 7.05 m (12H) 1.8 d (3H),
7.25 7.9 m (28H) 1.9 d (3H)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 5 2002
Knizhnikov
