1902
MATSURA et al.
prepared from palladium(II) tetraaqua complex by the
k3
procedure in [15]. Palladium black was obtained by
reduction of palladium(II) chloride dissolved in
hydrogen chloride with 20% aqueous hydrazine [16].
[
H Pd (CH =CHCH OH)].
(3)
I + III
m
n
2
2
k4
IV
Decomposition of intermediate IV results in forma-
tion of 1-propanol and regeneration of the catalyst
The reaction products were identified by gas
chromatography, gas chromatography mass spec-
trometry, and NMR.
[reaction (4)].
k5
IV
Pd + CH CH CH OH.
(4)
The kinetics of hydrogenation were studied
volumetrically by the absorption of a hydrogen gas
mixture according to the procedure described in [15].
The quantities of propenal and 2-methyl-2-pentenal
(II) formed were determined gravimetrically after the
aldehydes had been converted into the corresponding
n
3
2
2
The hydrogenation rate decreases as the concentra-
tion of allyl alcohol is increased over 0.1 M, probably
because reaction (5) occurs between compound I and
colloid palladium [9] along with reactions (2) (4).
2,4-dinitrophenylhydrazones [17].
k6
Pd + I
[Pd (CH =CHCH OH)].
(5)
n
n
2
2
The concentrations of gases in water were calcu-
lated using reference data [18].
k7
V
Obviously, compound V slower reacts with hydro-
gen than compound III with allyl alcohol. At the
same time, the formation of compound V makes
possible oxidation of allyl alcohol with oxygen.
ACKNOWLEDGMENT
The authors are grateful to members of the labora-
tory of Academician I.I. Moiseev (Institute of General
and Inorganic Chemistry) for providing the giant
palladium cluster.
The kinetics of the proposed mechanism of hydro-
genation of allyl alcohol should follow Arrhenius’s
temperature dependence. The negative temperature
effect observed in the present work may be associated
with structural changes in colloid palladium [10, 11]
at elevated temperatures, that adversely affect its
catalytic activity.
The work was financially supported by the Inter-
national Science and Technology Center (grant
no. 1281).
REFERENCES
As already noted, hydrogenation of allyl alcohol
concurs with its condensation (1) forming compound
II. The same reaction performed in the presence of
colloid palladium obtained by preliminary reduction
with hydrogen fails to provide compound II.
1. Matsura,V.A, Potekhin, V.V., and Ukraintsev, V.B.,
Zh. Obshch. Khim., 2002, vol. 72, no. 1, p. 113.
2
. Potekhin, V.V., Matsura, V.A., and Ukraintsev, V.B.,
Zh. Obshch. Khim., 2000, vol. 70, no. 6, p. 886.
Note that in the presence of the giant palladium
cluster Pd561Phen (OAc) [12] or palladium black
3. Dorfman, Ya.A. and Sokol’skii, D.V., Koordinatsia i
gidrirovanie na metallakh (Coordination and Hydro-
genation on Metals), Alma-Ata: Nauka, 1975, p. 215.
60
180
[13] reaction (2) does not occur. This finding suggests
that the active form of palladium, that catalyzes reac-
tion (2), is formed from palladium(II) tetraaqua
complex only when the latter is reduced in the pre-
sence both allyl alcohol and hydrogen. However, the
evidence in hand allows no justified conclusions as to
the mechanism of formation of compound II.
4
. Gomez-Bengoa, E., Naheda, P., and Echavarren, A.M.,
Tetrahedron Lett., 1994, vol. 35, no. 38, p. 7097.
5
. Ibragimova, D.I., Zhubanov, K.A., and Shumatae-
va, N.F., Gidrirovanie i okislenie na geterogennykh
katalizatorakh (Hydrogenation and Oxidation on
Heterogeneous Catalysts), Alma-Ata: Nauka, 1975,
p. 312.
The resulting data show that in the presence of
colloid palladium in situ allyl alcohol is hydrogenated
by the double bond and oxidized, like alkylaromatic
alcohols [1], by a carbon atom bearing the hydroxy
group.
6
7
. Kaneda, K., Fujii, M., and Marioka, K., J. Org. Chem.,
1
996, vol. 61, p. 4502.
. Kaneda, K., Fujii, M., and Ebitani, K., Tetrahedron
Lett., 1996, vol. 38, no. 52, p. 9023.
EXPERIMENTAL
8. Matsura, V.A., Potekhin, V.V., Platonov, V.V.,
Tatsenko, O.M., Ukraintsev, V.B., and Khokhrya-
kov, K.A., Zh. Obshch. Khim., 2003, vol. 73, no. 11,
p. 1767.
Palladium(II) tetraaqua complex was prepared by
the procedure in [14]. Colloid palladium in situ was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 12 2003