1374
TRACH et al.
activity of both binuclear V and triad VIII palladium
complexes points to a determining influence of the
metal nature on the catalytic activity of the complexes.
(2H, CH2, Allyl), 2.86 d (2H, CH2, Allyl), 2.82 d (2H,
CH2, Allyl). Found, %: C 40.21; Н 3.59; N 10.11.
C28H30Cl2N6Pd2Ru. Calculated, %: C 40.26; H 3.62; N
10.06.
The most active complex III in the series of
compounds under study was used for the determination
of the dependence of the 1-octene oxidation rate on the
catalyst concentration. The data obtained on carrying
out the reaction under the same conditions, but at a
lower temperature (313 K), are given below.
Conditions of measuring spectral characteristics of
the compounds see [4].
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 09-03-
90416-Ukr_f_a) and the State Foundation for Basic
Research of Ukraine (grant no. F28/256-2009).
III×105, mol l–1
2.5 7.5 38
75 220 500
W0×105, mol l–1 s–1
3.2 11.0 11.2 12.5 13.5 16.0
These data show that a high catalytic activity of
complex III is observed even at the concentration of
7.5×10–5 M and increases slightly as the temperature
increases further.
REFERENCES
1. Denisov, E.T. and Afanas’ev, I.B., Oxidation and
Antioxidants in Organic Chemistry and Biology, Boca
Raton, FL: CRC, Taylor and Francis, 2005, p. 981.
Complexes I–V and VII were synthesized by the
procedures [6–11].
2. Punniyamurthy, T., Velusamy, S., and Iqbal, J., Chem.
Rev., 2005, vol. 105, p. 2329.
3. Sheldon, R.A. and Kochi, J.K., Metal-Catalyzed
Oxidations of Organic Compounds, New York: Acad.
Press, 1981, p. 359.
4. Trach, Yu.B., Makota, O.I., Cherkasova, T.G.,
Gal’ding, M.R., and Varshavskii, Yu.S., Zh. Obshch.
Khim., 2010, vol. 80, no. 6, p. 1040.
5. Trach, Y.B., Bulgakova, L.V., Makota, O.I., Suprun, W.Ya.,
Schulze, B., and Stark, C.B.W., J. Mol. Catal., 2009,
vol. 302, p. 124.
[(Cod)Rh(µ-Cl2)Rh(PPh3)(CO)] (VI). To a weighed
sample of 0.106 g of [Rh(PPh3)(CO)Cl]2 [12] a solu-
tion of 0.185 g of [Rh(Cod)Cl]2 [13] in 6 ml of
chloroform was added. The suspension was stirred
with a magnetic stirrer up to complete dissolution of
the initial complex. The solvent was removed in vacuo,
a residue was ground with hexane at –30°С, filtered
off, washed with hexane (–30°С), and dried. Yield
0.27 g (92%). IR spectrum (CHCl3), cm–1: ν(CO) 1980.
1H NMR spectrum (CDCl3), δ, ppm: 4.42 (2H, CH,
Cod), 3.94 (2H, CH, Cod), ~2.5 m (4H, CH2, Cod),
~1.8 m (4H, CH2, Cod), 7.8–7.4 (15H, Ph, PPh3). 13C
6. McCleverty, J.A. and Wilkinson, G., Inorg. Synth.,
1966, vol. 8, p. 211.
2
NMR spectrum (CDCl3), δ, ppm: (1JCRh, JCP, Hz):
7. Varshavsky, Yu. S., Cherkasova, T.G., Podkorytov, I.S.,
Lyssenko K.A., and Nikol’skii, A.B., J. Organomet.
Chem., 2003, vol. 665, p. 156.
184.29 (CO, 81.3, 17.5). 31P NMR spectrum (CDCl3),
2
δ, ppm: (1JCRh, JCP, Hz): 46.48 (PPh3, 175.9, 17.5).
Found, %: C 47.79; Н 4.02; Cl 10.31. C27H27Cl2·
8. Powell, J. and Shaw, B.L., J. Chem. Soc., 1968, p. 583.
OPRh2. Calculated, %: C 48.03; H 4.03; Cl 10.05.
9. Glordano, G. and Crabtree, R.H., Inorg. Synth., 1979,
vol. 19, p. 218.
Complex VI in the CHCl3 solution is in a dynamic
equilibrium with initial complexes.
10. Yoshitaka, T., Toshikatsu, Y., and Seiotsuka, Inorg.
Synth., 1979, vol. 19, p. 220.
[(Allyl)ClPd(CN)Ru(Py)4(CN)PdCl(Allyl)] (VIII).
To a solution of 0.117 g of trans-[Ru(Py)4(CN)2] [14]
in 3 ml of chloroform a solution of 0.091 g of
[PdCl(Allyl)]2 [10] in 5 ml of chloroform was added.
The mixture was stirred for 15 min, then the solvent
was removed, the reaction product was carried on a
filter, washed with ether, and dried up in vacuo. Yield
0.198 g (95%). IR spectrum (CHCl3), cm–1: ν(CN)
2098. 1H NMR spectrum (CDCl3), δ, ppm: 8.58 d (8H,
CH, Py), 7.65 t (4H, CH, Py), 7.16 t (8H, CH, Py),
5.49 m (2H, СH, Allyl), 3.4 d (2H, CH2, Allyl), 3.89 d
11. Varshavsky, Yu.S., Cherkasova, T.G., Galding, M.R.,
Khrustalev, V.N., Podkorytov, I.S., Gindin, V.A., Smir-
nov, S.N., and Nikol’skii, A.B., J. Organomet. Chem.,
2009, vol. 694, p. 2917.
12. Varshavskii, Yu.S., Cherkasova, T.G., Kiseleva, N.V.,
Bresler, L.S., Buzina, N.F., and Khachaturov, A.S., Zh.
Neorg. Khim., 1985, vol. 30, no. 1, p. 152.
13. Chatt, J. and Venanzi, L.M., J. Chem. Soc., 1957,
no. 12, p. 4735.
14. Varshavskii, Yu. S. and Cherkasova, T.G., Zh. Obshch.
Khim., 2010, vol. 80, no. 2, p. 332.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010