Catalytic properties of rhodium organometallic complexes in the reaction of 1-octene oxidation with molecular oxygen

Full text of DOI:10.1134/S1070363210060290

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 6, pp. 1208–1209. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Yu.B. Trach, O.I. Makota, T.G. Cherkasova, M.R. Gal’ding, Yu.S. Varshavskii, 2010, published in Zhurnal Obshchei Khimii, 2010,
Vol. 80, No. 6, pp. 1040–1041.
LETTERS
TO THE EDITOR
Catalytic Properties of Rhodium Organometallic Complexes
in the Reaction of 1-Octene Oxidation with Molecular Oxygen
Yu. B. Tracha, O. I. Makotaa, T. G. Cherkasovab, M. R. Gal’dingb, and Yu. S. Varshavskiib
a Institute of Chemistry and Chemical Tecnologies, “L’vovskaya Politekhnika” National University, Lviv, Ukraine
b St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
e-mail: yurelv@gmail.com
Received November 10, 2009
DOI: 10.1134/S1070363210060290
The use of molecular oxygen, which is ecologically
pure and accessible oxidizing agent, for obtaining
oxygen-containing compounds by the oxidation of
hydrocarbons is a very attractive process from the
economic and ecological points of view. The
possibility of carrying out reactions of hydrocarbons
oxidation in mild conditions with a high rate, and also
an increase in selectivity of the reactions and, hence,
an increase in the target product yield are reached by
the use of catalysts capable of affecting various stages
of the complicated oxidation process: the initiation,
propagation, and termination of reaction chains [1-4].
333 K. Complex [Rh(Acac)(PPh3)(CO)] (II) is the
most active. Complexes of rhodium in the oxidation
states + 2 (XI) and +3 (XII) appeared much less active
that all complexes containing rhodium in the oxidation
state +1.
W0×105, mol l–1 s–1
Catalyst
Without a catalyst
[Rh(Acac)(CO)2] (I)
[Rh(Acac)(PPh3)(CO)] (II)
[Rh(Oxq)(CO)2] (III)
[Rh(Oxq)(PPh3)(CO)] (IV)
[Rh(Oxq)(DMSO)(CO)] (V)
[Rh(PhC(O)CHC(NH)Ph)(CO)2] (VI)
[Rh(PhC(O)CHC(NH)Ph)(PPh3)(CO)] (VII)
[Rh(CF3COO)(PPh3)2(CO)] (VIII)
[Rh(BPh4)(PPh3)2] (IX)
0.1
2.0
6.5
3.6
2.1
2.9
3.2
4.0
5.4
3.5
4.3
1.8
With the aim of searching for effective catalysts of
hydrocarbons oxidation by molecular oxygen we have
studied the effect of some rhodium organometallic
complexes on the initial rate (W0) of the oxidation of 1-
octene by molecular oxygen. Preliminary experiments
have shown that the studied complexes affect the
oxidation process only in the presence of hydroper-
oxides. In this work we used tert-butyl hydroperoxide.
The reaction was carried out in chlorobenzene, the
tert-butyl hydroperoxide concentration was 0.05 M,
and the catalyst concentration, 0.01 M; T 333 K; Acac,
Oxq, and OAc are singly charged residues of
acetylacetone, 8-hydroxyquinoline, and acetic acid,
respectively, Cod is 1,5-cyclooctadien, and DMSO,
dimethyl sulfoxide.
[Rh(BPh4)(Cod)] (X)
[Rh2(OAc)4(H2O)2] (XI)
Compounds I–IV and VIII–XI were synthesized
by the procedures [5–9] and compound XII, by the
procedure [10]; the synthesis of new compounds V–
VII is described below.
[Rh(Oxq)(DMSO)(CO)] (V). To a suspension of
[Rh(Oxq)(CO)2], 0.628 g in 10 ml of MeCN, a freshly
prepared solution Me3NO·2H2O, 0.230 g in 38 ml of
MeCN, was added dropwise at 0°C with stirring. The
reaction mixture was stirred for 1 h at room
temperature. The solvent was distilled off in a vacuum,
and the residue was dissolved again in MeCN (15 ml).
To thus obtained solution a solution of DMSO, 0.328 g
in 5 ml of MeCN, was added. Golden needle-like
crystals were filtered off, washed by diethyl ether, and
dried in a vacuum. The second fraction was obtained
The measured rates of the 1-octene oxidation
(W0×105, mol l–1 s–1) with various catalysts are given
below.
The results show that the systems (tert-butyl hydro-
peroxide–rhodium organometallic complex) exhibit a
high activity in the reaction of 1-octene oxidation at
1208

CATALYTIC PROPERTIES OF RHODIUM ORGANOMETALLIC COMPLEXES
1209
upon evaporation of the filtrate. Total yield 0.50 g
δ(13C) 77.0 ppm, δ(1H) of residual protons 7.25 ppm)
and reported with respect to TMS. The 31P chemical
shifts were measured from the external standard (85%
aqueous H3PO4).
1
(69%). IR spectrum (CHCl3), cm–1: ν(CO) 2000. H
NMR spectrum (CDCl3), δ, ppm: 8.5–6.5 (6H, Oxq),
3.41 (6H, DMSO). 13С NMR spectrum, δ, ppm (J, Hz):
188.28 (CO, 74.8). Found, %: C 40.58; H 3.47; N 3.93.
C12H12NO3RhS. Calculated, %: C 40.79; H 3.40; N
3.96.
Oxidation was carried out on a gasometric
installation [11] in a glass reactor with a temperature-
controlled jacket and a magnetic stirrer.
[Rh(PhC(O)CHC(NH)Ph)(CO)2] (VI). To
a
ACKNOWLEDGMENTS
solution of [Rh(CO)2Cl]2, 0.25 g in 10 ml of CHCl3,
PhC(O)CHC(NH2)Ph, 0.29 g, and Ba(CO)3, 0.6 g,
were added. The reaction mixture was stirred for 2 h at
room temperature, filtered, and the filtrate was
evaporated in a vacuum. The residue was dissolved in
diethyl ether, the solvent was distilled off, and the
residue was left in a freezing chamber at –20°С for
48 h. Yield 0.38 g (79%). Orange fine crystals. IR
spectrum (CНCl3), cm–1: ν(CO) 2072, 2004. 13С NMR
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).
REFERENCES
1
1. Emanuel’, N.M., Denisov, E.T., and Maizus, Z.K.,
Tsepnye reaktsii okisleniya uglevodorodov v zhidkoi
faze (Chain Reactions of the Oxidation of Hydrocarbons
in Liquid Phase), Moscow: Nauka, 1965.
spectrum (CDCl3), δ, ppm (J, Hz): 186.36 (CO, JCRh
2
3
1
71.4, JCC 8.9, JCH 2.9), 185.35 (CO, JCRh 64.5).
Found, %: C 53.91; Н 3.02; N 3.88; Rh 26.97.
C17H12NO3Rh. Calculated, %: C 53.56; Н 3.15; N
3.67; Rh 26.99.
2. Brégeault, J.-M., J. Chem. Soc., Dalton Trans., 2003,
p. 3289.
[Rh(PhC(O)CHC(NH)Ph)(PPh3)(CO)] (VII). To
a solution of complex (VI), 0.183 g in 20 ml of
benzene, PPh3, 0.13 g, was added. The solution was
stirred for 30 min. The solvent was distilled off in a
vacuum; the residue was treated by hexane and held in
a freezing chamber at –20°С for several days. Yield
0.39 g (81%). Yellow fine crystals. The substance
consists of a mixture of isomers. IR spectrum (CНCl3),
cm–1: ν(CO), 1968. In the prevailing isomer (>90%)
PPh3 is in the trans-position to the nitrogen atom. 13С
NMR spectrum (CDCl3), δ, ppm (J, Hz): 190.3 (СO,
3. Denisov, E.T. and Afanas’ev, I.B., Oxidation and
Antioxidants in Organic Chemistry and Biology, Boca
Raton, FL: CRC, Taylor and Francis, 2005.
4. Punniyamurthy, T., Velusamy, S., and Iqbal, J., Chem.
Rev., 2005, vol. 105, p. 2329.
5. Varshavskii, Yu.S. and Cherkasova, T.G., Zh. Neorg.
Khim., 1967, vol. 12, no. 6, p. 1709.
6. Varshavskii, Yu.S., Cherkasova, T.G., Buzina, N.A.,
Knyazeva, N.N., and Ionina, T.I., Zh. Neorg. Khim.,
1970, vol. 15, no. 3, p. 715.
7. Varshavskii, Yu.S., Cherkasova, T.G., Podkorytov, I.S.,
Korlyukov, A.A., Khrustalev, V.N., and Nikol’skii, A.B.,
Koord. Khim., 2005, vol. 31, no. 2, p. 132.
2
3
1JCRh 75.1, JCP 22.2, JCH 2.0). 31P NMR spectrum
1
(CDCl3), δ, ppm (J, Hz): 41.5 (PPh3, JCRh 149.3).
Found, %: C 66.81; Н 4.10; N 2.02; Rh 16.59.
C34H27NO2PRh. Calculated, %: C 66.35; Н 4.39; N
2.27; Rh 16.72.
8. Shestakova, E.P., Varshavskii, Yu.S., Khrustalev, V.N.,
and Podkorytov, I.S., J. Organomet. Chem., 2007,
vol. 692, p. 4297.
9. Varshavskii, Yu.S., Cherkasova, T.G., Nikol’skii, A.B.,
and Vorontsov, I.I., Zh. Neorg. Khim., 2001, vol. 46,
no. 5, p. 777.
The IR spectra were measured on a Specord-75IR
31
1
spectrometer. The 13С, P, and H NMR spectra were
measured on a DPX-300 spectrometer for solutions in
CDCl3, working frequencies 75, 120, and 300 MHz,
10. Fedorov, I.A., Rodii (Rhodium), Moscow: Nauka, 1966,
1
respectively. The 13С and H chemical shifts were
p. 201.
11. Tsepalov, V.F., Zavod. Lab., 1964, no. 1, p. 111.
measured in relation to the internal standard (CDCl3,
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