SYNTHESIS AND HYDROPHOSPHORYLATION OF -COMPLEXES
871
2.5 h and then treated with hexane. The precipitate
was filtered off on a glass frit to obtain a light yellow
fine crystalline powder, yield 40%, decomp. point
enoylphosphate)]tungsten(0) (VIIb). Tetracarbonyl-
4-methyl cinnamate)tungsten(0), 0.15 g, was dis-
(
solved in 5.0 ml of absolute degassed benzene, and
0.2 ml of diethyl hydrogen phosphite was added. The
reaction mixture was kept for 24 h at room tempera-
ture under argon and then its 31P NMR spectrum was
measured. The solvent was removed in a water-jet-
pump vacuum to concentrate 4 5 times. The light
green crystals that formed were filtered off under
argon to obtain white fine crystals, yield 15%,
1
111 113 C. IR spectrum, , cm : 1550 (coordinated
C=C), 1680 (C=O of free methyl acrylate), 2100,
2020, 1940, 1900, 1880 (carbonyl ligands on
1
tungsten). H NMR spectrum, , ppm: 3.45-3.35 m
(coordinated CH2=CH). 13C NMR spectrum, C, ppm:
45 s (coordinated =CH), 49 s (coordinated CH2=).
Pentacarbonyl( 2-methyl acrylate)chromium(0),
pentacarbonyl( 2-methyl cinnamate)tungsten(0),
1
decomp. point 88 94 C. IR spectrum, , cm : 1580
(coordinated C=C), 1680 (free ester C=O), 2010, 1970,
1950, 1910 (carbonyl ligands on tungsten), 1300 br
pentacarbonyl( 2-methyl cinnamate)chromium(0),
pentacarbonyl( 2-dimethyl fumarate)chromium, and
pentacarbonyl( 2-dimethyl fumarate)tungsten(0)
were obtained by the same procedure. The yield of
the organometallic products decreases in the series
methyl cinnamate, methyl acrylate, and dimethyl
fumarate.
1
(coordinated P=O). H NMR spectrum, , ppm: 4.00
3.85 m (coordinated CH=CH). 31P NMR spectrum,
P, ppm: 0.29 (JPW 34 Hz). 31P NMR spectrum of
the reaction mixture also contained a signal at
127 ppm (JPW 310 Hz). During isolation, this signaPl
fully disappeared and quantitatively converted to a
Tetracarbonyl( 4-methyl cinnamate)tungsten(0)
(IIIc). A solution of 0.5 g of hexacarbonyltungsten(0)
in 20 ml of acetonitrile was refluxed under argon.
Methyl cinnamate, 0.260 g, was then added, and the
resulting mixture was refluxed for 14 h. The solvent
was removed in a water-jet-pump vacuum without
heating to concentrate the reaction mixture 4-5 times.
The light green crystals that formed were filtered off
under argon. A fine crystalline light green powder was
obtained, yield 45%, decomp. point 138 141 C. IR
signal at
0.29 ppm.
P
REFERENCES
1. Schmidt, T., Chem. Ber. Rev., 1997, vol. 138,
pp. 453 461.
2. Knolker, H.-J., Chem. Rev., 2000, vol. 100, no. 8,
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3. Pape, A.R., Kaliappan, K.P., and Kundig, E.P., Chem.
Rev., 2000, vol. 100, no. 8, pp. 2917 2940.
1
spectrum, , cm : 1580 (coordinated C=C), 1600
(coordinated methyl cinnamate C=O), 2100, 2020,
1
4. Kuramshin, A.I., Karpenko, E.A., and Cherka-
sov, R.A., Zh. Obshch. Khim., 1999, vol. 69, no. 7,
pp. 1221 1222.
1900, 1880 (carbonyl ligands on tungsten). H NMR
spectrum, , ppm: 4.00-3.85 m (coordinated CH=CH).
13C NMR spectrum, C, ppm: 43 s (=CH-COCH3),
49 s (coordinated Ph-CH=).
5. Kuramshin, A.I., Karpenko, E.A., and Cherka-
sov, R.A., Zh. Obshch. Khim., 2001, vol. 71, no. 2,
pp. 215 220.
Tetracarbonyl( 4-methyl cinnamate)chromium(0)
and tetracarbonyl( 4-methyl cinnamate)molybde-
num(0) were obtained analogously.
6. Kuramshin, A.I., Gazizov, A.S., Kuramshina, E.S.,
and Cherkasov, R.A., Zh. Obshch. Khim., 2000,
vol. 70, no. 8, pp. 1384 1385.
Bis( 2-methyl acrylate)tetracarbonyltungsten(0)
(IVc). A solution of 0.5 g of hexacarbonyltungsten(0)
in 20 ml of acetonitrile was refluxed for 40 min under
argon. Methyl acrylate, 0.260 g, was then added, and
the resulting mixture was refluxed for 14 h. The
solvent was removed in a water-jet-pump vacuum
without heating to concentrate the reaction mixture
4 5 times. The light green crystals that formed were
filtered off under argon to obtain a fine crystalline
powder, yield 45%, decomp. point 138 141 C. IR
7. Pastor, A., Galindo, A., Guttierrez-Puebla, E., and
Monge, A., J. Organomet. Chem., 1998, vol. 566,
pp. 211 216.
8. Berke, H., Huttner, G., Sontag, C., and Zsolnai, L.,
Z. Naturforsch. B, 1985, vol. 40b, pp. 799 807.
9. Rusik, C.A., Collins, M.A., Gamble, A.S., Ton-
ker, T.L., and Templeton, J.L., J. Am. Chem. Soc.,
2001, vol. 111, no. 18, pp. 2550 2560.
1
spectrum, , cm : 1550, 1530 (coordinated C=C);
1675 (free methyl acrylate C=O), 2100, 2020, 1900,
1880 (carbonyl ligands on tungsten). H NMR spec-
trum, , ppm: 5.25 4.38 (coordinated CH2=CH).
1
10. Kuramshin, A.I., Karpenko, E.A., and Cherka-
sov, R.A., Zh. Obshch. Khim., 2001, vol. 71, no. 3,
pp. 221 225.
Tetracarbonyl[ 3-(diethyl 3-phenylprop-2-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 6 2004