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Development of polysilane-supported palladium/alumina hybrid catalysts and

their application to hydrogenation
Hidekazu Oyamada,a Takeshi Naito,a Shinpei Miyamoto,a Ryo Akiyama,a,b Hiroyuki Hagioa and
Shu Kobayashi*a,b
Received 3rd October 2007, Accepted 13th November 2007
First published as an Advance Article on the web 23rd November 2007
DOI: 10.1039/b715220e

Novel immobilized Pd catalysts, polysilane-supported pal- conrmed by ICP analysis when nitrogen-containing compounds
ladium/alumina hybrid catalysts, have been developed. The such as nitrobenzene were used. Furthermore, these catalysts had a
catalysts showed high catalytic activity for hydrogenation, somewhat limited applicability prole, since the carrier polysilane
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and could be used in an organic solvent or under solvent-free dissolved in some organic solvents. In order to address these
conditions. issues, we planned to apply the PI method to polysilane-supported
catalysts. In this paper, we describe the synthesis of highly active PI
Palladium is one of the most important hydrogenation catalysts Pd/PSi on aluminium oxide and its application to hydrogenation.
used in both laboratories and industry. While immobilized palla- We rst examined several metal oxides and the ratio to
dium (Pd) catalysts such as Pd/C and Pd/SiO2 , etc. have been often Pd/PSi for the preparation of hybrid catalysts (Table 1). In a
employed, leaching of the palladium from the supports, moderate typical procedure, poly(methylphenyl)silane (M w = 3.2 104 ) and
yields of recovery, contamination of the reaction products with Pd(OAc)2 were combined in THF at 0 C for 1 h, and a metal oxide
palladium, and poisoning of the catalyst by heteroatoms such as was added to this mixture. After stirring for a further 1 h, MeOH
sulfur and nitrogen, etc. are sometimes serious problems especially was added to form microencapsulated Pd (MC Pd/PSi) on the
in the manufacture of pharmaceuticals.1 To address these issues, metal oxide. The resulting MC Pd/PSi (1) was heated at 140 C
new methods for the immobilization of homogeneous Pd catalysts for 2 h, washed sequentially with THF, CHCl3 , and MeOH, and
onto inorganic or organic supports have been widely investigated.2 dried under reduced pressure to afford PI Pd/PSi on the metal
However, tedious procedures are often needed for the preparation oxide 2. We tested hybrid catalysts 2 on the hydrogenation of
of such heterogeneous catalysts, and lower activity/selectivity and ethyl cinnamate (Scheme 1). When SiO2 was used, recovery of
leaching of catalysts from the supports remain serious problems. palladium was low (Table 1, entry 2). On the other hand, Al2 O3 ,
Previously, we have developed new methods for immobilizing TiO2 , and ZrO2 gave promising results (entries 3, 6 and 9). It
metal catalysts onto polymers, microencapsulation3 and polymer was found that higher ratios of the metal oxides to Pd/PSi were
incarcerated (PI) protocols,4 which are based on physical envel- important for good recovery of palladium and high activity for
opment by the polymers, and electronic interaction between p the hydrogenation (entries 4, 5, 8, 10, and 11).
electrons of the benzene rings of the polystyrene-based polymers
and vacant orbitals of the metals. Next, we focused on polysilanes
as a support for heterogeneous catalysts. Polysilanes have been
widely studied due to their interesting electronic properties such
as high hole mobility, photoconductivity, and nonlinear optical
properties caused by r-conjugation of the silicon backbone.57 In
addition, polysilane is used as a starting material for ceramics Scheme 1 Hydrogenation of ethyl cinnamate
and synthetic methods for mass production are established.8
Recently, we have synthesized immobilized Pd and Pt catalysts Among the metal oxides tested, alumina was revealed to be
based on poly(methylphenyl)silane for the rst time.9 Polysilane- superior to other metal oxides in terms of yield and quality of the
supported Pd catalysts (Pd/PSi) have been successfully used in immobilized catalysts (entries 4 and 5). With these data in hand,
hydrogenation. The reactions proceeded in high yields, and the we further studied preparation conditions of the catalyst using
catalysts could be recovered and reused almost quantitatively alumina. In a large-scale preparation of PI Pd/PSi, it was found
by simple ltration. Polysilane-supported Pt (Pt/PSi) catalysts that the heating at 140 C under neat conditions (cross-linking
were prepared by a similar method and showed high activity step) gave low reproducibility, presumably due to irregularity of
in hydrosilylation. However, a small amount of Pd leaching was heating and inuence of oxygen. After further investigations, good
reproducibility was obtained when decane was used as a solvent
a under an argon atmosphere. Next, several conditions for the cross-
Department of Chemistry, School of Science and Graduate School of
Pharmaceutical Sciences, The University of Tokyo, The HFRE Division, linking step were examined (Table 2). It was found that whilst
ERATO, Japan Science and Technology Agency (JST), Hongo, Bunkyo- palladium catalysts 4 that had been prepared at 120 C and 140 C
ku, Tokyo, 113-0033, Japan for 2 hours gave quantitative conversion in the hydrogenation
b
Science of Process Laboratories, ERATO, Japan Science and Technology
reaction, those prepared over a longer period of time gave lower
Agency (JST), Matoba, Kawagoe, Saitama, 350-1101, Japan. E-mail:
shu_kobayashi@chem.s.u-tokyo.ac.jp; Fax: +81 3 5684 0634; Tel: +81 3 conversions in the subsequent hydrogenation (entries 2 and 4). On
5841 4790 the other hand, using a preparation temperature of 160 C even

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Table 1 Preparation of PI Pd/PSi on metal oxide and hydrogenation reaction

Preparation of PI Pd/PSi on metal oxide Hydrogenationa

Entry Metal oxide (g) Yield of 1 (g) Yield of 2/1 (w/w) Loading/lmol g1 Recovery of Pd (%)b Conversion (%)c Leaching (%)d

1 None 0.72 13.4 96 94 NDf

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2 SiO2 (1.0) 1.81 0.56 49.8 51 88 0.27

3 Al2 O3 (1.0) 1.63 0.77 72.3 91 55 0.23
4 (5.0) 5.62 0.95 15.1 81 99.8 <0.28
5 (10.0) 10.57 0.96 8.3 85 99.8 <0.28
6 TiO2 (1.0) 1.63 0.79 60.1 78 74 <0.23
7 (5.0) 5.61 0.99 11.7 65 76 <0.28
8 (10.0) 10.56 0.97 7.3 74 >99.9 <0.28
9 ZrO2 (1.0) 1.60 0.80 63.7 81 46 <0.23
10 (5.0) 5.61 0.93 16.2 90 99.3 <0.28
11 (10.0) 10.48 0.91 8.2 79 >99.9 <0.30
a
Reaction conditions: see Scheme 1. b Recovery over two steps. c Determined by GC analysis. d Determined by ICP analysis. e MC Pd/PSi was used. f Not
determined.

Table 2 Preparation of PI Pd/PSi on Al2 O3 by the heat cross-linking method and hydrogenation reaction

Hydrogenationa
Preparation of PI Pd/PSi on Al2 O3 Conversion (%)c
Entry x/ C y/h Yield of 4/3 (w/w) Loading/lmol g1 Recovery of Pd (%)b 1h 2h Leaching (%)d

1 120 2 0.91 15.2 80 94 Quant. <0.74

2 120 4 0.91 12.7 67 74 93 1.06
3 140 2 0.93 15.8 85 73 Quant. <0.74
4 140 4 0.93 16.3 89 59 94 <0.74
5 160 2 0.95 15.3 84 63 82 <0.74
a
Reaction conditions: ethyl cinnamate (1 mmol), Pd catalyst 4 (0.1 mol%), EtOH (1 mL) and H2 (1 atm), rt, 2 h. b Recovery of two steps. c Determined
by GC analysis. d Determined by ICP analysis.

over the shortened time of 2 hours only afforded a catalyst whose While N-methylmaleimide, maleic acid, and a diene were reduced
activity was comparatively low (entry 5). smoothly to afford N-methylsuccinimide, succinic acid, and alkane
The substrate scope of the hydrogenation was then examined in high yields, respectively, a small amount of Pd leaching was
using 0.05 mol% PI Pd/PSi on alumina (4a) in organic solvents observed (entries 4, 5 and 6). Furthermore, in the case of using
such as ethanol and dichloromethane under hydrogen gas at at- catalyst 4a, nitrobenzene was reduced smoothly to afford aniline
mospheric pressure and room temperature (Table 3). Gratifyingly quantitatively. It is particularly noteworthy that the leaching of Pd
it was found that under these conditions ethyl cinnamate (entry 1) in this instance was lower than that observed when using the MC
and 2-cyclohexen-1-one (entry 2) were reduced smoothly in EtOH Pd/PSi catalyst (entries 7 and 8).
to afford the desired products in high yields without leaching of We also evaluated catalyst 4a in the hydrogenation of ethyl
Pd. Chalcone also reacted smoothly to give the corresponding cinnamate, N-methylmaleimide, and chalcone using 0.05 or
ketone and alcohol in 91% and 6% yields, respectively (entry 3). 0.20 mol% of Pd under solvent-free conditions (Table 4).10 We

62 | Org. Biomol. Chem., 2008, 6, 6165 This journal is The Royal Society of Chemistry 2008
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Table 3 Substrate scope

Entry Substrate Solvent Conc./mol L1 Time/h Product Yield (%)b Leaching (%)c

1 EtOH 0.33 1 >99.9d <0.22

2 EtOH 1.0 4 Quant. <0.30

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3 EtOH 1.0 24 91 (6) 0.99

4 EtOH 0.50 1 97 0.48

5 EtOH 1.0 3.5 Quant. 0.94

6 CH2 Cl2 0.50 24 98 3.6

7 EtOH 1.0 8 >99.9d 0.34

8e Hexane 0.33 1.5 >99.9d 2.28

a
Pd: 0.142 wt%, Al: 47.7 wt%, Si: 2.28 wt% (determined by ICP analysis). b Determined by 1 H NMR analysis. c Determined by ICP analysis. d Conversion,
determined by GC analysis. e 0.50 mol% of MC Pd/PSi without Al2 O3 was used. See ref. 9

Table 4 Hydrogenation without solvent

Entry Substrate 4a/mol% Temp. Time/h Product Yield (%)a Leaching (%)b

1 0.05 RT 8 >99.9c <0.22

2d 0.05 50 C 16 Quant.e <0.10

3 0.05 50 C 1 58
4 0.20 RT 1 79

5 0.05 50 C 24 80 (Trace)
6 0.20 50 C 24 95 (5) 0.12

a
Determined by 1 H NMR analysis. b Determined by ICP analysis. c Conversion, determined by GC analysis. d 25 mmol scale. e Determined by GC analysis

had previously found that when using MC Pd/PSi with a liquid that in the case of 4a, the reaction could be conducted without
chemical such as ethyl cinnamate as substrate, the catalyst was leaching of Pd (entries 1 and 2). Solid chemicals such as
dissolved in the substrate and the palladium metal tended to N-methylmaleimide and chalcone could be used as substrates
leach from the support. Pleasingly however, it was discovered directly and good chemical yields were obtained (entries 3, 4, 5

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and 6). Particularly, in the case of chalcone, it is noted that the solvent or under solvent-free conditions. Further investigations
leaching of Pd was lower than that observed when using ethanol to prepare other immobilized metal catalysts as well as their
as a solvent (entry 6, cf. Table 3, entry 3). applications to other reactions are now in progress.11
In order to probe the structure of the catalyst, we analyzed PI
catalyst 4 (Table 2, entry 3) by 29 Si CPMAS NMR (Fig. 1). In
the preparation of MC Pd/PSi on alumina (3), while a portion Notes and references
of the SiSi bonds were oxidized to form OSiO bonds, almost Synthesis of poly(methylphenylsilane): Methylphenyldichlorosilane
the same signals (chart c) as for those of poly(methylphenylsilane) (382 g, 2.00 mol) was added dropwise to a suspension of sodium (96.6 g,
(chart a) were observed. On the other hand, PI Pd/PSi on alumina 4.20 mol) in THF (1 L) over 30 min with vigorous stirring at reux
temperature. After stirring for further 3.5 h, the mixture was cooled in
[catalyst 4 (Table 2, entry 3)] gave interesting spectra (chart d). an ice bath and diluted with toluene (500 mL). 3 N HCl (500 mL) was
29
Si NMR analysis revealed four signals at about 100, 40, added dropwise to the mixture, the organic layer was separated, and water
33, and 25 ppm, corresponding to SiOAl, SiSi, OSiO, was added to the aqueous layer to dissolve NaCl. The aqueous layer
was extracted with toluene and the combined organic layers were washed
and SiOSi bonds, respectively. It was assumed that polysilane
with H2 O, 5% aqueous solution of NaHCO3 , H2 O and brine. The organic
was xed on activated alumina by formation of linkages with layer was dried over Na2 SO4 and concentrated to ca. 600 mL in vacuo.
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aluminium through oxygen. In addition, since alumina has a lot MeOH (750 mL) was added to the solution, the precipitate was collected
of nanopores on the surface, it is expected that the polysilane- by ltration and washed with MeOH. The crude polysilane was dissolved
in toluene (370 mL) and precipitated by adding iPrOH. The precipitate
supported palladium clusters are included in these nanopores and was collected, washed with tolueneiPrOH (1 : 5) and dried under reduced
stabilized. However, at the current time the precise structure of pressure at 55 C to afford poly(methylphenylsilane) (135 g, 56% yield).
catalyst 4 is still unclear, and further investigation and information M w = 3.21 104 , M n = 1.12 104 , M w /M n = 2.87.
are needed. General procedure for the preparation of PI Pd/PSi on Al2 O3 (4) (Table 2):
Poly(methylphenylsilane) (100 g) was dissolved in THF (800 mL) and
cooled to 0 C. To this solution, palladium(II) acetate (2.25 g, 10.0 mmol)
was added and the mixture was stirred for 1 h at this temperature. To the
dark brown polymer solution was added alumina (500 g), and the mixture
was allowed to warm to room temperature. After 2 h, MeOH (4 L) was
slowly added for coacervation and the resulting precipitate was collected
by ltration, washed with MeOH several times and dried under reduced
pressure at 55 C to afford the microencapsulated palladium catalyst (MC
Pd/PSi on Al2 O3 3, 581 g, Pd = 14.3 mmol g1 , 83% of Pd was loaded).
The Pd loading was determined by ICP analysis. MC catalyst 3 (20 g) was
suspended in decane (40 mL) at room temperature, and heated to 120
160 C for 24 h. The resulting solid was collected by ltration, washed
with hot THF and MeOH several times and dried under reduced pressure
at 55 C. The polymer incarcerated palladium catalysts (PI Pd/PSi on
Al2 O3 4) were obtained. The loading of Pd was determined by ICP analysis.
Hydrogenation catalyzed by PI Pd/PSi on Al2 O3 (4a) (Table 3): A
typical experimental procedure is described for the hydrogenation of
ethyl cinnamate. Ethyl cinnamate (5 mmol) and PI Pd/PSi on Al2 O3 (4a,
0.05 mol%) were combined in ethanol (15 mL). The mixture was stirred
for 1 h at room temperature under H2 atmosphere (1 atm). The yield and
conversion were determined by GC analysis with reference to naphthalene
or 1 H NMR analysis with reference to 1,2,3,4-tetramethylbenzene (durene)
as an internal standard. The leaching of Pd from the support was
determined by ICP analysis.

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