Synthesis of new mixed-ligand cationic complexes of palladium [(acac)Pd(PPh3)(L)]BF4

Full text of DOI:10.1134/S107036321104030X

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 779–780. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © D.S. Suslov, V.S. Tkach, M.V. Bykov, M.V. Belova, O.I. Mis’ko, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 4,
pp. 689–690.
LETTERS
TO THE EDITOR
Synthesis of New Mixed-Ligand Cationic Complexes
of Palladium [(acac)Pd(PPh3)(L)]BF4
D. S. Suslov, V. S. Tkach, M. V. Bykov, M. V. Belova, and O. I. Mis’ko
Irkutsk State University, ul. K. Marksa 1, Irkutsk, 664003 Russia
e-mail: tkach@chem.isu.ru
Received April 22, 2010
DOI: 10.1134/S107036321104030X
A selection of ligands, including mono-, bi-, and
tridentate ones containing phosphorus, nitrogen, sulfur,
oxygen, or a combination of them, is an important part
of the practice of homogeneous catalysis of the
reactions of unsaturated hydrocarbons by the transition
metal complexes [1, 2]. While comparing the reactivity
of neutral and cationic complexes, the preference was
given to the latter [3, 4]. In a series of the transition
metals, the palladium complexes are extensively used
as active and selective catalysts for conversion of the
unsaturated hydrocarbons over 50 years [5]. A
common characteristic of the known synthetic methods
of the cationic palladium complexes used as catalysts
or components of catalytic systems is a multistage
process and the use of expensive starting reagents
including the silver salt of AgA type (where A is
anion), thallium salts, or triphenylmethyl tetrafluoro-
borate [2, 6, 7]. In [8–10] we described a method for
the synthesis of cationic palladium complexes [(acac)
Pd(PAr3)2]BF4 in one stage by the reaction of Pd(acac)2,
PAr3, and BF3OEt2 in 1:2:2 molar ratio. The testing of
the catalytic system [(acac)Pd(PAr3)2]BF4/BF3OEt2
showed its high activity and selectivity (100%) in the
process of styrene dimerization [8] and additive poly-
merization of norbornene [11].
This publication presents the results of the synthesis
of a new series of cationic palladium complexes
[(acac)Pd(PPh3)(L)]BF4, where L is HNEt2, HNBu2, or
PBu3. The proposed approach expands essentially the
potential of the synthesis of mixed-ligand cationic
complexes of palladium.
O
O
O
O
L
O
L, HBF4·OEt2, toluene
_acacH, _OEt2
Pd
BF4
Pd
PPh3
O
PPh3
(Acetylacetonato-k2O,O')diethylamino(triphenyl-
phosphine)palladium tetrafluoroborate (I). To a mix-
ture of 0.4355 g (0.768 mmol) of Pd(Acac)2PPh3 and
0.0562 g (0.08 ml) of NHEt2 in toluene was added
dropwise 1 ml of 10 vol % of HBF4·OEt2 solution in
CH3NO2 at room temperature under argon. The
mixture was stirred for 2–3 h. The yellow precipitate
formed. The solution was decanted, the precipitate was
washed thrice with toluene. Yield 0.2323 g (48%). IR
spectrum, ν, cm–1: 1526, 1567 (C=O+C=C, acac), 689,
706, 745 (C–H, PPh3), 1047, 1092 (B–F, BF4), 3200
(N–H), 2953, 2986 (С–H, NHEt2). 13С NMR spectrum,
δC, ppm: 10 (CH3), 26 (CH3), 43 (CH2), 100 (СH),
126–135 (Ph), 186 (C=O). Found, %: С 50.63; H 6.26.
C27H33BF4NO2PPd. Calculated, %: С 51.66; H 5.30.
(Acetylacetonato-k2O,O')dibutylamino(triphenyl-
phosphine)palladium tetrafluoroborate (II) was pre-
pared similarly. Yield 0.1600 g (32%). IR spectrum, ν,
cm–1: 1523, 1565 (C=O+C=C, acac), 685, 715, 740
779

780
SUSLOV et al.
(C–H, PPh3), 1050, 1090 (B–F, BF4), 3200–3300 (N–H),
2967, 2942, 2880 (С–H, NHBu2). 13С NMR spectrum,
δ, ppm: 11 (CH3), 19 (CH2), 26 (CH3), 48 (CH2), 100
(СH), 126-135 (Ph), 186 (C=O). Found, %: С 54.47; H
6.94. C31H41BF4NO2PPd. Calculated, %: С 54.45; H
6.04.
Program “Scientific and scientific-pedagogical stuff on
the innovational Russia” on the 2009–2013 years, state
contract no. P1488).
REFERNCES
(Acetylacetonato-k2O,O')tributylphosphino(tri-
phenylphosphine)palladium tetrafluoroborate (III).
To a solution of 0.48 g (0.846 mmol) of Pd(acac)2PPh3
in 15 ml of toluene was added 0.78 ml of 1 M tributyl-
phosphine solution in toluene at room temperature
under argon. Then to this mixture was added dropwise
1 ml of 10 vol % HBF4·OEt2 solution in OEt2. The
reaction mixture was stirred for 1 h and concentrated at
40°С in a vacuum. The precipitate was washed with
diethyl ether and dried in a vacuum. Yield 0.3 g (52%).
IR spectrum, ν, cm–1: 1520, 1558 (C=O+C=C, acac),
687, 742 (C–H, PPh3), 1048, 1090 (B–F, BF4), 3200–
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31
2870, 2927, 2959 (С–H, PBu3). P NMR spectrum, δ,
8. Tkach, V.S., Suslov, D.S., Rokhin, A.V., Shmidt, F.K.,
ppm: 26.5 (PBu3), 35.7 (PPh3). Found, %: С 54.47; H
6.94. C35H49BF4O2P2Pd. Calculated, %: С 54.54; H 6.52.
Zh. Obshch. Khim., 2007, vol. 77, no. 4, p. 694.
13
31
9. Tkach, V.S., Suslov, D.S., Myagmarsuren, G., Ratov-
skii, G.V., Rokhin, A.V., Tuczek, F., and Shmidt, F.K.,
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The C and P were registered on a Varian VXR-
500S spectrometer in СH3NO2. The IR spectra were
recorded on a Infralum FT-801 instrument.
10. Tkach, V.S., Suslov, D.S., Rokhin, A.V., and Shmidt, F.K.,
RF Patent no. 2329269, 2008.
ACKNOWLEDGMENTS
11. Tkach, V.S., Suslov, D.S., Myagmarsuren, G., and
Shmidt, F.K., RF Patent no. 2383556, 2008.
This work was supported by the Russian Federation
Ministry of Education and Science (the Federal Target
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 4 2011