Communications
systems at the Data Processing Center of Kyoto University according
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to a previously reported procedure.[25]
Received: November 13, 2004
Revised: December 29, 2004
Published online: April 28, 2005
[17] See the Supporting Information for typical time courses for the
oxidation of 1.
Keywords: alcohols · heterogeneous catalysis · oxidation ·
ruthenium · supported catalysts
.
[18] A control experiment was performed using benzaldehyde in the
presence of RuMn2/HT and water at 608C in toluene under
oxygen. Benzaldehyde was quantitatively recovered showing
that it is not oxidized further under these conditions. See
Supporting Information.
[19] RuMn2/HT is highly effective for the oxidation of benzylic and
aromatic allylic alcohols, but not for primary aliphatic alcohols;
the oxidation of 1-octanol with RuMn2/HT (2 mol-% Ru)
afforded octanal in 62% yield at 608C after 5 h. A CoCeRu
trimetallic catalyst shows a high activity for the aerobic oxidation
of primary aliphatic alcohols: H.-B. Ji, T. Mizugaki, K. Ebitani,
K. Kaneda, Tetrahedron Lett. 2002, 43, 7179; K. Ebitani, H.-B. Ji,
T. Mizugaki, K. Kaneda, J. Mol. Catal. A 2004, 212, 161.
[20] 1) The addition of a radical scavenger (2,6-di-tert-butyl-p-cresol)
did not affect the rate of the oxidation. 2) Treatment of RuMn2/
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Prins), Wiley, New York, 1988.
ꢀ
HT with 1 under argon afforded an IR signal of a Ru H species
at 2120 cmꢀ1 [10,16d]
.
This species disappeared upon exposure to
O2. 3) During the oxidation of 1, the ratio of O2 consumed to 2
was 1:2.
[21] R. W. Missen, C. A. Mims, B. A. Saville, Introduction to Chem-
ical Reaction Engineering and Kinetics, Wiley, New York, 1999.
The initial rate of oxidation of 1 is proportional to the amount of
RuMn2/HT and independent of the oxygen pressure.
[22] If the second step in Equation (1) is the rate-determining step,
the KM value can be regarded as a dissociation equilibrium
constant (kꢀ1/k1) of the first step. See ref. [21].
[23] A similarly high chemoselectivity for primary alcohols has been
observed in the Zr(OAc)2-catalyzed oxidation of alcohols: K.
Kaneda, Y. Kawanishi, S. Teranishi, Chem. Lett. 1984, 1481.
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[26] H. W. Baur, Acta Crystallogr., Sect. B 1976, 32, 220.
[10] See Supporting Information.
[11] P. Triggs, Helv. Phys. Acta 1985, 58, 657.
ꢀ
ꢀ
[12] Two Ru O bonds of 1.83 and 2.07 ꢀ are assigned to Ru OH and
ꢀ
Ru OH2, respectively. See: P. Dubourdeaux, M. Tavarꢄs, A.
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ꢀ
[13] The Mn Mn distance is slightly shorter than that in bis-
(hydroxo)-bridged MnIV dimers (2.73–2.93 ꢀ). See: M. J. Bald-
win, T. L. Stemmler, P. J. Riggs-Gelasco, M. L. Kirk, J. E.
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[14] Generation of heterometallic species has not been reported on
HT containing Pd, Os, or W.[7c]
[15] For selected heterogeneous Ru catalysts for alcohol oxidation,
see: a) M. Matsumoto, M. Watanabe, J. Org. Chem. 1984, 49,
3435; b) K. Yamaguchi, K. Mori, T. Mizugaki, K. Ebitani, K.
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Baiker, Chem. Rev. 2004, 104, 3037 as a recent review.
[16] For representative aerobic alcohol oxidations by homogeneous
metal complexes, see: a) A. Hanyu, E. Takezawa, S. Sakaguchi,
3426
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Angew. Chem. Int. Ed. 2005, 44, 3423 –3426