Pd nanoparticles on reverse phase silica gel as recyclable catalyst for Suzuki-Miyaura cross coupling reaction and hydrogenation in water

Article abstract of DOI:10.1016/j.jorganchem.2017.07.003

Two catalytic systems, consisting of palladium nanoparticles supported by reverse phase amino functionalized silica are utilized as catalysts for Suzuki-Miyaura reaction and hydrogenation in water. The catalysts were developed by modifying silica into bidentate ligands, using either 2-pyridinecarboxaldehyde or 2,2′-bipyridine-4,4′-dicarboxylic acid. The synthesized catalysts showed quantitative reaction yields and recyclability with negligible leaching of Pd nanoparticles. Various characterization techniques including XPS, ICP-MS, SEM, BET, XRD, TEM, ¹H- and ¹³C- NMR are used to verify the efficiency of the catalysts.

Full text of DOI:10.1016/j.jorganchem.2017.07.003

Accepted Manuscript
Pd nanoparticles on reverse phase silica gel as recyclable catalyst for Suzuki-Miyaura
cross coupling reaction and hydrogenation in water
Saira Shabbir, Sinyoung Lee, Minkyung Lim, Heejin Lee, Hyeji Ko, Youngbok Lee,
Hakjune Rhee
PII:
S0022-328X(17)30425-4
10.1016/j.jorganchem.2017.07.003
JOM 20017
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 31 March 2017
Revised Date: 29 June 2017
Accepted Date: 4 July 2017
Please cite this article as: S. Shabbir, S. Lee, M. Lim, H. Lee, H. Ko, Y. Lee, H. Rhee, Pd
nanoparticles on reverse phase silica gel as recyclable catalyst for Suzuki-Miyaura cross coupling
reaction and hydrogenation in water, Journal of Organometallic Chemistry (2017), doi: 10.1016/
j.jorganchem.2017.07.003.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Pd nanoparticles on reverse phase silica gel as recyclable catalyst for
Suzuki-Miyaura cross coupling reaction and hydrogenation in water
a,c
b
b
b
c
b,c
Saira Shabbir, Sinyoung Lee, Minkyung Lim, Heejin Lee, Hyeji Ko, Youngbok Lee, and Hakjune
Rhee *
b,c
a
Department of Chemistry, Quaid-i-Azam University, Islamabad,45320, Pakistan.
Department of Bionanotechnology, Hanyang University, Sangnok-gu, Hanyang daehak-ro 55,
b
Ansan, Gyeonggi-do 15588, Korea
c
Department of Applied Chemistry, Hanyang University, Sangnok-gu, Hanyang daehak-ro 55,
Ansan, Gyeonggi-do 15588, Korea
*
Corresponding author. Tel.: +82 31 400 5498; Fax: +82 31 400 5457.
E-mail address: hrhee@hanyang.ac.kr
Abstract
Two catalytic systems, consisting of palladium nanoparticles supported by reverse phase amino
functionalized silica are utilized as catalysts for Suzuki-Miyaura reaction and hydrogenation in water. The
catalysts were developed by modifying silica into bidentate ligands, using either 2-pyridinecarboxaldehyde or
2
,2′-bipyridine-4,4′-dicarboxylic acid. The synthesized catalysts showed quantitative reaction yields and
recyclability with negligible leaching of Pd nanoparticles. Various characterization techniques including XPS,
1
13
ICP-MS, SEM, BET, XRD, TEM, H- and C- NMR are used to verify the efficiency of the catalysts.
Keywords: Palladium; heterogeneous catalyst; recycle; cross-coupling; reverse phase silica; hydrogenation.
1

ACCEPTED MANUSCRIPT
1
. Introduction
Palladium catalysis, whether by Suzuki-Miyaura coupling reaction that introduces a C-C bond between
organoboranes and halide species,[1] or hydrogenation reaction involving the catalytic reduction of unsaturated
hydrocarbons,[2] has a great influence on synthetic organic chemistry. For example, palladium-catalyzed cross
couplings form the backbone of pharmaceutical plants[3] and many other industries.[4] Green chemistry
considerations generally favor heterogeneous reactions over homogeneous reactions for palladium catalysis.[5]
Using water as a reaction medium also helps to ensure environmentally friendly conditions.[6] However, the
choice of solid support is crucial.
A variety of solid supports have been assessed for this purpose including zeolites,[7] polymers,[8] oxides,[9]
metal organic frameworks,[10] and silica.[11] Among these, silica has generated the most interest because of its
chemical and thermal stability, and adaptability to different organic catalytic systems with the aid of variable
porosity.[12] The use of traditional heterogeneous supports is limited by coagulation of palladium nanoparticles,
and sensitivity to air and moisture.[13] Considering the importance of silica as a support, organic reactions in
water have also been reviewed and categorized.[14] Recent efforts have been directed towards the use of
functionalized silica that can stabilize the metal on support by complexation as in the case of 1,3-
dicyclohexylguanidine functionalized SBA-15 mesoporous silica[15] and imine functionalized silica.[16]
In this study, we have synthesized two types of silica-supported Pd(0) catalysts. One is 2-
pyridinecarboxaldehyde ligand which is anchored onto commercially available 3-aminopropyl-fuctionalized
silica gel (APPd(0)@Si). The other has bipyridyl ligand on starting material, 3-aminopropyl-fuctionalized silica
gel (BPPd(0)@Si). These ligands were developed on reverse phase silica by selective modification of
functional groups. Amino-functionalized reverse phase silica with alkyl end capped amino groups was used to
induce hydrophobic behavior in the polar silica support. This work is intended to support green chemistry, so
catalysis was planned with the use of water as a solvent. Utilizing water as a reaction medium with a
hydrophobic catalyst support, ensures the close proximity of organic reactants to catalyst active sites. It also
helps to discourage the use of phase transfer catalysts as well as toxic and expensive organic solvents.
2
. Results and Discussion
2
.1. Preparation of palladium catalysts.
2

ACCEPTED MANUSCRIPT
Before coordinating Pd(II) with silica, we modified the functionalized silica with two kinds of bidentate
ligands. Synthesis of the first is aided by imine formation with the reaction of amino functional silica and 2-
pyridine carboxaldehyde. After coordinating the developed imino functional silica with Pd(OAc) , IPPd(II)@Si
2
was obtained. The reduction of Pd(II) to palladium nanoparticles was carried out and was signaled by a change
in the color from brown to black. The reduction of Pd(II) at this stage yielded APPd(0)@Si consisting of Pd
nanoparticles held by a 5-membered palladacycle. The other type of bidentate ligand was synthesized from
amino-functional reverse phased silica and 2,2'-bipyridine-4,4'-dicarboxylic acid chloride. Coordination of the
ligand with Pd(OAc) , followed by reduction to Pd nanoparticles, produced the BPPd(0)@Si catalyst (Scheme
2
1
). The synthesized catalysts have been studied by SEM, TEM and EDXA (Figure 1). The average size of the
nanoparticles is around 3 nm and 4 nm for APPd(0)@Si and BPPd(0)@Si catalysts, respectively.
The insight into ligands structure is obtained by solid-state NMR experiments of the starting 3-aminopropyl
functionalized silica, and iminopropyl and bipyridyl functionalized silica ligands. The loading values of Pd(0)
are 0.540 mmol/g of APPd(0)@Si and 0.598 mmol/g of BPPd(0)@Si, according to inductively coupled plasma-
mass spectrometric analysis (ICP-MS).
Scheme 1. Overall schematics of APPd(0)@Si and BPPd(0)@Si catalyst synthesis.
Figure 1. (a) Scanning electron microscope (SEM) image. (b) Transmission electron microscope (TEM) image. (c) & (d)
Energy dispersive X-ray analysis (EDXA) of APPd(0)@Si and BPPd(0)@Si catalysts.
3

ACCEPTED MANUSCRIPT
BET (Brunnauer-Emmet-Teller) and XRD (X-ray diffraction) analyses were also performed (included in SI).
As a result of BET, the catalysts have a pore size of 6-8 nm similar to that of the commercially available
3
3
functionalized 3-aminopropyl silica gel, and the pore volume was 0.395 cm /g and 0.386 cm /g for APPd(0)
and BPPd(0), respectively. XRD pattern demonstrates that the catalysts have diffraction peaks of Pd(0).[17]
2
.2. Application to Suzuki-Miyaura coupling reactions
The catalysts IPPd(II)@Si and APPd(0)@Si, were tested for Suzuki-Miyaura coupling reaction of 4-
bromoacetophenone and phenylboronic acid. Interestingly, both catalysts resulted in a quantitative coupling
product yield at moderate temperatures, such as 60 °C. However, a recycling test clearly distinguished between
the two catalysts. APPd(0)@Si retained its catalytic efficiency after recycling, while IPPd(II)@Si failed to
reproduce the original results. The explanation lies in the change of oxidation state and subsequent leaching of
palladium from the silica support. This conclusion was supported by X-ray photoelectron spectroscopy (XPS)
analysis that shows a clear reduction of Pd(II) to Pd(0) after recycling IPPd(II)@Si (Figure 2).
200000
180000
160000
140000
120000
100000
180000
160000
Pd 3d
Pd 3d
1
1
1
40000
20000
00000
Pd(II)
Pd(0)
Pd(II)
Pd(II)
Pd(0)
Pd(II)
8
6
0000
0000
8
0000
0000
0000
0000
0
6
4
2
40000
20000
0
3
60
355
350
345
340
335
330
325
320
3
60
355
350
345
340
335
330
325
320
Binding energy (eV)
Binding energy (eV)
Figure 2. X-ray photoelectron spectroscopy (XPS) analysis of IPPd(II)@Si before and after recycling.
To maintain the oxidation state of Pd(II) in IPPd(II)@Si, a range of oxidative additives including tert-
butylhydroperoxide (TBHP), p-benzoquinone, H O , Cu(OAc) , K S O were tested with IPPd(II)@Si catalyst.
2
2
2
2
2
8
However, reaction yields were still low compared to APPd(0)@Si due to leaching of palladium from
IPPd(II)@Si into the reaction medium. Therefore, we focused on APPd(0)@Si and compared it with the
standard palladium-charcoal catalyst and found it to be more efficient in catalyzing Suzuki-Miyaura coupling
reaction. To find an appropriate solvent, several experiments were performed using either dioxane, water, or a
mixture of the two solvents dioxane and water in different ratios (5:1, 3:1, 1:1). It was observed that increasing
4

ACCEPTED MANUSCRIPT
the ratio of the organic solvent had a negative effect on the reaction progress. Reactions catalyzed in water
showed excellent yields, as was already anticipated based on the affinity of the organic substrate to the
hydrophobic catalyst in the aqueous phase.
[a]
Table 1. Optimization of Suzuki-Miyaura Cross Coupling reaction
[
b]
[c]
[d]
Oxidant
Temp.
(°C)
Time
(h)
Conversion
TON
TOF
Entry
Catalyst
Solvent
-
1
(
mmol)
SM:P (%)
(mol/mol)
(h )
1
2
IPPd(II)@Si
-
H O
60
60
1
1
0:100
100
100
2
Recycled
IPPd(II)@Si
-
H O
2
11:89
89
89
3
4
IPPd(II)@Si
IPPd(II)@Si
TBHP (1)
TBHP (0.1)
H O
60
60
1
1
34:67
9:90
67
90
67
90
2
H O
2
p-Benzoquinone
5
IPPd(II)@Si
H O
2
60
1
90:2
2
2
(
1)
6
7
8
9
IPPd(II)@Si
IPPd(II)@Si
IPPd(II)@Si
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
H O (1)
H O
60
60
60
25
25
60
70
80
90
1
1
49:47
83:11
85:12
97:2
47
11
12
2
47
11
12
2
2
2
2
Cu(OAc) (1)
H O
2
2
K S O (1)
H O
2
1
2
2
8
-
-
-
-
-
-
H O
2
1
1
1
1
1
1
0
1
2
3
4
H O
2
24
1
74:18
7:91
18
91
98
99
100
0.8
91
98
99
100
H O
2
H O
2
1
1:98
H O
2
1
1:99
H O
2
1
0:100
Dioxane:H O
2
1
1
1
5
6
7
8
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
APPd(0)@Si
-
-
-
-
80
80
80
80
1
1
0:100
34:66
57:42
4:93
100
66
100
66
(
1:1)
Dioxane:H O
2
(
3:1)
Dioxane:H O
2
1
42
42
(
5:1)
Dioxane:H O
2
1
1
24
93
3.9
(
5:1)
9
0
APPd(0)@Si
Pd-C
-
-
Dioxane
80
80
1
1
100:0
39:53
0
0
2
[
H O
2
53
53
a] Reaction conditions: 4-Bromoacetophenone (1 mmol), phenylboronic acid (1.5 mmol), K CO (3 mmol), H O (6 mL) and
catalyst (1 mol%). [b] Calculated by H-NMR. [c] Reactant moles converted/catalyst moles. [d] TON/reaction time.
2
3
2
1
Further support for this conclusion was obtained by the addition of organic solvent to the reaction mixture,
which resulted in dilution by removing organic substrates from the catalyst, thereby showing the reaction
progress. Therefore, we consider water to be the best solvent for the catalytic system under study. To optimize
5

ACCEPTED MANUSCRIPT
the reaction temperature, experiments were performed at temperatures ranging from room temperature to a
maximum of 90 °C. A moderate temperature of 80 °C was found to be ideal (Table 1).
Various bromoarenes and arylboronic acids were subjected to Suzuki-Miyaura coupling reaction and found
to actively produce the corresponding biphenyls (Table 2). Reactions were facilitated by the presence of the
electron withdrawing group on the bromoarenes, and were deactivated in the presence of electron donating
substituents like 4-methoxy or 4-amino groups. 1-Bromo-4-nitrobenzene and 4-bromobenzonitrile, have a low
solubility in water, so a mixture of dioxane and water was used as a solvent and nearly quantitative product
yields were observed.
In the case arylboronic acid with an electron withdrawing group, biphenyls were obtained almost
quantitatively with the exception of 4-nitrophenylboronic acid, which reacted passively under the optimized
reaction conditions due to its limited solubility in water.
[a]
Table 2. Substrate scope of Suzuki-Miyaura cross coupling reaction
[b]
Entry
1
1 (R1)
2 (R2)
Product 3
Time(h) Yield(%)
1a (-H)
2a (-H)
4
Quant.
2
3
4
5
1b (-NH2)
1c (-OH)
2a
2a
2a
2a
16
82
1
24
5
98
90
1d (-OCH3)
1e (-CH3)
Quant.
6
7
1f (-CHO)
2a
2a
3
1
97
99
O
1g (-COCH3)
3
g
6

ACCEPTED MANUSCRIPT
8
1h (-COOCH3)
1i (-CN)
2a
3
99
Quant.
92
[c]
9
2a
2a
0.5
0.5
[
c]
1
0
1j (-NO2)
1
1
1g
1g
1g
1g
1g
2b (-COOCH3)
2c (-NO2)
2d (-Cl)
3
24
1
76
43
[c]
1
2
1
3
4
5
99
1
1
2e (-OCH3)
2f (-CH3)
9
93
10.5
Quant.
[
a] Reaction conditions: Bromoarene (1 mmol), arylboronic acid (1.5 mmol), K CO (3 mmol), H O (6 mL)
2 3 2
and APPd(0)@Si catalyst (1 mol%), 80 °C. [b] Isolated yield. [c] Solvent mixture: Dioxane/H O = 3 mL/3 mL.
2
Recycling tests were carried out using recycled catalysts, showing little or no change in the product
yield (87% - Quant.) (Table 3). Note that some difference in the yields is inevitable, arising from
slight differences in the amount of catalyst recovered each time. The filtrate was checked for evidence
of palladium leaching and palladium was not detected.
[a]
Table 3. Recycling test of APPd(0)@Si catalyst for Suzuki-Miyaura cross coupling reaction
[b]
Run
1 (R1)
2 (R2)
Product 3
Time (h)
1
Yield (%)
99
st
1
1
g (-COCH3)
2a (-H)
7

ACCEPTED MANUSCRIPT
nd
rd
2
1
1
1
1
Quant.
97
1
1
1
1
g
g
g
g
2a
2a
2a
2a
3g
3g
3g
3g
3
4
5
th
th
99
94
th
th
6
7
1
3
Quant.
98
1
c (-OH)
2a
2a
1h (-COOCH3)
1f (-CHO)
1a (-H)
th
th
8
9
3
95
2
a
2f (-CH3)
0.5
1
91
87
th
1
0
1
g
2a
3g
[
a] Reaction conditions: Bromoarene (1 mmol), arylboronic acid (1.5 mmol), K CO (3 mmol), H O (6 mL) and
2 3 2
APPd(0)@Si catalyst (1 mol%). [b] Isolated yield.
2
.3. Application to Hydrogenations
BPPd(0)@Si and APPd(0)@Si catalysts were used for the hydrogenation of trans-cinnamic acid
and similar compounds. Optimization of reaction conditions was done by testing a variety of available
bases at different temperatures. A comparison of the newly developed catalysts with commercial
palladium-charcoal was also made. Potassium hydroxide (KOH) proved to be a good choice of base
under the prevailing reaction conditions, as opposed to potassium carbonate (K CO ). 5.0 mol% of
2
3
BPPd(0)@Si showed better catalytic activity for hydrogenation than 5.0 mol% of Pd/C, indicated by
quantitative and 45% product yields, respectively (Table 4). Most of the starting materials and reaction
products have similar R values in thin layer chromatography (TLC), so reaction progress was
f
1
monitored by H-NMR. Reaction parameters including catalyst loading and the base were adjusted to
give insight into the reaction and optimize reaction conditions. Both APPd(0)@Si and BPPd(0)@Si
were found to be equally active for the hydrogenation of olefins.
8

ACCEPTED MANUSCRIPT
[a]
Table 4. Optimization of reaction conditions for hydrogenation catalyzed by BPPd(0)@Si and APPd(0)@Si catalysts
[c]
[d]
TON
TOF
[b]
Entry
4 (R , R , R )
Catalyst (mol%)
Base
Time (h) SM:P (%)
1
2
3
-1
(mol/mol)
(h )
1
2
3
4
5
6
7
8
9
4a (-H, -COOH, -H)
BPPd(0)@Si (1)
BPPd(0)@Si (3)
BPPd(0)@Si (5)
APPd(0)@Si (5)
BPPd(0)@Si (5)
BPPd(0)@Si (5)
Pd/C (5)
KOH
KOH
KOH
KOH
0.5
0.5
0.5
0.5
0.5
1
37:63
13:87
0:100
0:100
19:81
0:100
50:45
42:58
52:47
0:100
0:100
63
29
126
58
4a
4a
4a
4a
20
40
20
40
K CO3
2
16.2
20
32.4
20
4b (-H, -COCH , -H)
-
-
-
-
-
-
3
4b
1
9
9
4c (-H, -CH OH, -H)
BPPd(0)@Si (5)
APPd(0)@Si (5)
BPPd(0)@Si (5)
APPd(0)@Si (5)
0.5
0.5
2
11.6
9.4
20
23.2
18.8
10
2
4c
4c
4c
1
1
0
1
2
20
10
1
[
[
a] Reaction condition: Starting material (1 mmol), base (1 mmol), H O (5 mL). [b] Calculated by H-NMR.
c] Reactant moles converted/catalyst moles. [d] TON/reaction time.
2
Examination of various α,β-unsaturated carbonyl compounds as substrates for the hydrogenation
reaction was carried out (Table 5). It was observed that when the unsaturated carboxylic acids were
subjected to hydrogenations, the reaction went to completion very smoothly and efficiently. However,
some carboxylic acids in solid state soluble or sparingly soluble in water. Therefore, a mixture of
acetonitrile and water was used to obtain the saturated product. All of the unsaturated esters, ketones
and alcohols in the liquid phase were hydrogenated with >95% product yield. The only passive
reactants were trans-chalcone and p-methoxychalcone, which were only sparingly soluble in the
reaction medium and gave a mixture of ketone and alcohol as products.
[a]
Table 5. Hydrogenation substrate scope using BPPd(0)@Si catalyst in water
[b]
Entry
4 (R , R , R )
Product 5
Time (h)
Yield (%)
1
2
3
9

ACCEPTED MANUSCRIPT
[
c]
1
2
3
4
5
4a (-H, -COOH, -H)
0.5
1
99
97
[c]
[c]
[c]
[c]
4d (-H, -COOH, -CH3)
4e (-o-CH , -COOH, -H)
1
Quant.
96
3
OH
O
OH
4f (-o-OH, -COOH, -H)
1
5
f
4g (-o-OCH , -COOH, -H)
1
Quant.
99
3
6
4b (-H, -COCH , -H)
1
3
O
O
7
8
4h (-H, -COOCH , -H)
1
2
3
95
95
3
5h
4c (-H, -CH OH, -H)
2
[d]
[f]
9
4i (-H, -COPh, -H)
74:26
[e]
[g]
1
0
4j (-p-OCH , -COPh, -H)
3
69:31
3
[
[
[
(
(
a] Reaction condition: olefin (1 mmol), catalyst (5 mol% of Pd), H O (5 mL). [b] Isolated yield.
2
c] Potassium hydroxide (1 mmol) was used. [d] Solvent mixture: H O/CH CN = 4/1 (v/v).
2
3
e] Solvent mixture: H O/CH CN = 1/4 (v/v). [f] PhCH(OH)(CH ) Ph (26%) was also obtained
2
3
2 2
1
calculated by H-NMR). Selectivity for 5i was 48%. [g] PhCH(OH)(CH ) C H OCH (31%) was also obtained
calculated by H-NMR). Selectivity for 5j was 38%.
2
2
6
4
3
1
After the reaction, catalysts were collected and set aside for recycling experiments. Both
APPd(0)@Si and BPPd(0)@Si were tested for their recycling ability. In addition, the filtrate was
checked for evidence of palladium leaching. Fortunately, ICP-MS showed no significant loss of
palladium from either catalyst (Table 6).
1
0

ACCEPTED MANUSCRIPT
[a]
Table 6. Recycling test of BPPd(0)@Si and APPd(0)@Si catalyst for hydrogenation
[b]
Yield (%)
Run
4 (R , R , R )
Product 5
Time (h)
1
2
3
BPPd(0)Si
APPd(0)Si
99
st
1
4b (-H, -COCH , -H)
1
96
3
nd
2
4b
4b
4b
4b
4b
4b
4b
5b
5b
5b
5b
5b
5b
5b
1
1
1
1
1
1
1
Quant.
Quant.
95
98
97
rd
3
th
4
98
th
5
89
98
th
6
94
92
th
7
Quant.
Quant.
96
th
8
Quant.
th
9
4h (-H, -COOCH , -H)
1
99
97
3
th
1
0
4c (-H, -CH OH, -H)
2
Quant.
Quant.
2
[
a] Reaction condition: olefin (1 mmol), catalyst (5 mol% of Pd), H O (5 mL). [b] Isolated yield.
2
3
. Conclusions
We have successfully developed Pd(0) catalysts using end-capped reverse phase silica, in
accordance with green chemistry techniques. Reverse phase 3-aminopropyl-functionalized silica has
been modified to facilitate the reaction as well as anchor the metal firmly. The catalysts were
successfully applied to Suzuki-Miyaura cross coupling reaction as well as hydrogenation of various
unsaturated olefins. One of the most attractive features of the catalyst is their excellent recyclability,
regardless of the number of previous recycle tests carried out.
4
. Experimental
1
1

ACCEPTED MANUSCRIPT
4
.1. Materials and methods
All chemicals were purchased from commercial sources (Sigma Aldrich & TCI) and used without
any further purification, unless specifically mentioned. Solvents were dried and distilled by standard
procedures. The silica support used to prepare the catalysts, is the commercially available 9%
functionalized 3-aminopropyl silica gel with 1 mmol NH /gram (Particle size 40-63 µm; pore size 60
2
2
Å; surface area 550 m /g).
4
.2. Characterization
Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) measurements
were performed on a HRTEM JEOL electron microscope at an acceleration voltage of 300 kV while
transmission electron microscope (TEM) experiments were carried out using a Jeol JEM 2100F Field
Emission Electron Microscope. The loading value of Pd(0) and Pd(II) in the catalysts was estimated
by inductively coupled plasma (ICP) analysis with a JY Ultima2C. ICP analysis was also used to
check for leaching of Pd after the recycle test. X-ray photoelectron spectroscopy (XPS) analysis was
performed on a VG SCIENTA R3000. 1H-NMR spectra were recorded on a Bruker 400 MHz
1
3
instrument using CDCl as a solvent. For solid-state NMR experiments, 1D C spectra were
3
measured by cross polarization (CP) pulse sequence (contact time: 2 ms) on a Bruker 400 MHz NMR
spectrometer equipped with a 4 mm magic angle spinning (MAS) probe (Bruker Biospin, Billerica,
MA) operated at a 10 kHz spinning rate. Low temperature nitrogen adsorption-desorption isotherms
o
were measured at -196 C on an absorption volumetric analyzer BEL MINI manufactured by BEL, Inc.
(Japan). The specific surface area was determined using the Brunnauer-Emmet-Teller (BET) method from
nitrogen adsorption isotherms of the gas adsorbed at the relative pressure P/P0 = 0.99. X-ray diffraction (XRD)
1
2

ACCEPTED MANUSCRIPT
was obtained by an X-ray diffractometer from Bruker (D2 PHASER) using Cu Kα irradiation at 10 mA and
o
β0kV for 2θ in the range of 10-90 .
4
.3. Preparation of APPd(0)@Si catalyst
3-Aminopropyl functionalized silica gel (1.0 equiv., 5 g) was added to a 50 mL round bottom flask
containing a solution of 2-pyridinecarboxaldehyde (1.1 equiv., 0.523 mL) in 20 mL of distilled
CH Cl . After 3 hours of vigorous stirring, the reaction mixture was filtered, washed with CH Cl , and
2
2
2
2
dried under vacuum at 40 °C. To coordinate Pd(II) with silica, imine functionalized silica (1.0 equiv.,
.0 g) and Pd(OAc) (1.1 equiv., 0.68 g) were added to 20 mL of distilled CH Cl . The reaction
3
2
2
2
mixture was stirred at room temperature for 3 hours, followed by filtration, washing by CH Cl and
2
2
drying under vacuum at 40 °C. Pd(II) in the collected material was reduced by treating the collected
Pd(II) at silica (1.0 equiv., 3.4 g) with NaBH (9.0 equiv., 0.9 g), in 25 mL of dry distilled MeOH. The
4
catalyst APPd(0)Si was filtered after 12 hours, washed with MeOH and H O, and dried under vacuum
2
oven at 40 °C. The loading value of Pd in APPd(0)@Si was found to be 0.540 mmol Pd/g of the
catalyst.
4
.4. Preparation of BPPd(0)@Si catalyst
2,2'-Bipyridine-4,4'-dicarboxylic chloride was synthesized from 4,4'-dimethyl-2,2'-bipyridine by the
standard procedure.[18] To load the ligand onto silica, triethylamine (2.5 equiv., 2.51 mL) was slowly
added to the solution of 2,2'-bipyridine-4,4'-dicarboxylic acid chloride (0.6 equiv., 1.313 g) in 40 mL
distilled CH Cl . After the dissolution of the ligand in triethylamine, 3-aminopropylfunctionalized
2
2
silica gel (1.0 equiv., 7.2 g) was added to the mixture and stirred vigorously at room temperature
under argon. After 3 hours, the reaction mixture was filtered, washed with CH Cl , and dried under
2
2
vacuum at 40 °C. To coordinate Pd(II) with silica, the functionalized silica (1.0 equiv., 6.0 g) and
1
3

ACCEPTED MANUSCRIPT
Pd(OAc) (0.6 equiv. 0.73 g) were added to 48 mL of distilled CH Cl . The reaction mixture was
2
2
2
stirred at room temperature for 3 hours followed by filtration, washing by CH Cl and drying under
2
2
vacuum at 40 °C. Pd(II) in the collected material was reduced by treating the collected Pd(II) at silica
1.0 equiv., 3.4 g) with NaBH (9.0 equiv., 0.9 g), in 25 mL of dry distilled MeOH. The catalyst
(
4
BPPd(0)@Si was filtered after 12 hours, washed with MeOH and H O, and dried under vacuum at
2
4
0 °C. The loading value of Pd in BPPd(0)@Si was found to be 0.598 mmol Pd/g of the catalyst.
4
4
.5. Application to Suzuki-Miyaura coupling reactions
.5.1. General procedure for the Suzuki-Miyaura coupling reaction
In a typical Suzuki-Miyaura coupling reaction experiment, a 20 mL vial jacket was charged with
bromobenzene (1 mmol, 0.157 g), phenylboronic acid (1.5 mmol, 0.183 g) and K CO (3 mmol, 0.415
2
3
g) in 6 mL H O. After the addition of APPd(0)@Si catalyst (1 mol%, 0.019 g), the reaction mixture
2
was stirred at 80 °C for 4 hours. The reaction was monitored by thin layer chromatography (TLC).
After completion, the reaction mixture was cooled and 6 mL of ethyl acetate was added, followed by
filtration, and washing with 10 mL of ethyl acetate and H O. The ethyl acetate layer was collected and
2
dried with anhydrous magnesium sulfate and dried over in vacuo. The product was purified by silica-
gel column chromatography and analyzed by 1H NMR spectroscopy.
4
.5.2. 1,1'-Biphenyl (3a, Table 2, entry 1)
1
H NMR (400 MHz, CDCl ): δ 7.60 (d, J = 8.4 Hz, 4H), 7.44 (t, J = 7.1 Hz, 4H), 7.39-7.31 (m, 2H).
3
CAS Number: 92-52-4.
4
.5.3. 4-Amino-1,1'-biphenyl (3b, Table 2, entry 2)
1
H NMR (500 MHz, CDCl ): δ 7.58-7.51 (m, 2H), 7.43-7.37 (m, 4H), 7.29-7.23 (m, 1H), 6.75 (d, J
3
=
8.1 Hz, 2H), 3.71 (br s, 2H). CAS Number: 92-67-1.
1
4

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4
.5.4. 4-Hydroxy-1,1'-biphenyl (3c, Table 2, entry 3)
1
H NMR (500 MHz, CDCl ): δ 7.58-7.51 (m, 2H), 7.49 (d, J = 7.8 Hz, 2H), 7.42 (t, J = 7.1 Hz, 2H),
3
7
.30 (m, 1H), 6.91 (d, J = 7.8 Hz, 2H), 4.81 (s, 1H). CAS Number: 92-69-3.
4
.5.5. 4-Methoxy-1,1'-biphenyl (3d, Table 2, entry 4)
1
H NMR (500 MHz, CDCl ): δ 7.57-7.50 (m, 4H), 7.42 (d, J = 7.5 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H),
3
6
.98 (d, J = 8.7 Hz, 2H), 7.25 (d, J = 7.8Hz, 2H), 3.85 (s, 3H). CAS Number: 613-37-6.
4
.5.6. 4-Methyl-1,1'-biphenyl (3e, Table 2, entry 5)
1
H NMR (500 MHz, CDCl ): δ 7.58 (d, J = 6.6 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.42 (t, J = 7.4
3
Hz, 2H), 7.36-7.30 (m, 1H), 7.25 (d, J = 7.8 Hz, 2H), 2.39 (s, 3H). CAS Number: 644-08-6.
4
.5.7. 4-Formyl-1,1'-biphenyl (3f, Table 2, entry 6)
1
H NMR (500 MHz, CDCl ): δ 10.06 (s, 1H), 7.97 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 8.1 Hz, 2H),
3
7
.64 (d, J = 7.5 Hz, 2H), 7.50-7.42 (m, 3H). CAS Number: 3218-36-8.
4
.5.8. 4-Acetyl-1,1'-biphenyl (3g, Table 2, entry 7)
1
H NMR (400 MHz, CDCl ): δ 8.04 (d, J = 8.1 Hz, 2H), 7.69 (d, J = 9.0 Hz, 2H), 7.63 (d, J = 7.8
3
Hz, 2H), 7.46-7.40 (m, 3H), 2.64 (s, 3H). CAS Number: 92-91-1.
4
.5.9. 4-(Methoxycarbonyl)-1,1'-biphenyl (3h, Table 2, entry 8)
1
H NMR (500 MHz, CDCl ): δ 8.11 (d, J = 8.4 Hz, 2H), 7.67-7.61 (m, 4H), 7.46-7.38 (m, 3H), 3.94
3
(s, 3H). CAS Number: 720-75-2.
4
.5.10. 4-Cyano-1,1'-biphenyl (3i, Table 2, entry 9)
1
H NMR (500 MHz, CDCl ): δ 7.75-7.68 (m, 4H), 7.62-7.56 (m, 2H), 7.52-7.47 (m, 2H), 7.44-7.40
3
(m, 1H).CAS Number: 2920-38-9.
1
5

ACCEPTED MANUSCRIPT
4
.5.11. 4-Nitro-1,1'-biphenyl (3j, Table 2, entry 10)
1
H NMR (500 MHz, CDCl ): δ 8.30 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.2
3
Hz, 2H), 7.52-7.46 (m, 3H). CAS Number: 92-93-3.
4
.5.12. Methyl 4'-acetyl-1,1'-biphenyl-4-carboxylate (3k, Table 2, entry 11)
1
H NMR (400 MHz, CDCl ): δ 8.12-8.15 (m, 2H), 8.04-8.07(m, 2H), 7.68-7.72 (m, 4H), 3.95 (s,
3
3
H), δ 2.65 (s, 3H). CAS Number: 525362-25-8.
4
.5.13. 4-Acetyl-4'-nitro-1,1'-biphenyl (3l, Table 2, entry 12)
1
H NMR (400 MHz, CDCl ): δ 8.33 (d, J = 8.0 Hz, 2H), 8.10 (d, J = 8.0 Hz, 2H), 7.82(d, J = 8.0
3
Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H), 2.67 (s, 3H). CAS Number: 135-69-3.
4
.5.14. 4-Acetyl-4'-chloro-1,1'-biphenyl (3m, Table 2, entry 13)
1
H NMR (400 MHz, CDCl ): δ 8.03 (d, J = 8.3 Hz, 2H), 7.65 (d, J = 8.3 Hz, 2H), 7.56 (d, J = 8.3
3
Hz, 2H), 7.44 (d, J = 8.3 Hz, 2H), 2.64 (s, 3H). CAS Number: 5002-07-3.
4
.5.15. 4-Acetyl-4'-methoxy-1,1'-biphenyl (3n, Table 2, entry 14)
1
H NMR (400 MHz, CDCl ): δ 7.99 (d, J = 8.3 Hz, 2H), 7.63 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.3
3
Hz, 2H), 6.99 (d, J = 8.3 Hz, 2H), 3.84 (s, 3H). CAS Number: 13021-18-6.
4
.5.16. 4-Acetyl-4'-methyl-1,1'-biphenyl (3o, Table 2, entry 15)
1
H NMR (400 MHz, CDCl ): δ 7.54−7.48 (m, 2H), 7.39 (t, J = 7.6 Hz, 2H), 7.23 (s, 4H), 2.41 (s,
3
3
H), 2.01 (s, 3H). CAS Number: 5748-38-9.
4
.5.17. Recycling tests of Pd catalyst in Suzuki-Miyaura coupling reactions
Various Suzuki-Miyaura coupling reactions were carried out. The Suzuki-Miyaura coupling
reactions were performed as described above (Table 3). After the first reaction was complete, catalyst
1
6

ACCEPTED MANUSCRIPT
was recovered by hot filtration and air-dried. The recovered catalyst was successively subjected to the
next runs of the coupling reaction under the same reaction conditions as the first run.
4
4
.6. Application to hydrogenations
.6.1. General procedure for hydrogenations
In a typical hydrogenation experiment, trans-cinnamic acid (1.0 mmol, 0.148 g), catalyst
BPPd(0)@Si (5 mol%, 0.0836 g), and KOH (1.0 equiv., 5 mL 0.2 M solution) were added to the
reaction flask under hydrogen gas (1 atm). The reaction mixture was stirred at room temperature for
3
0 minutes followed by catalyst filtration and washing with 10 mL of water and ethyl acetate. The pH
was adjusted to 2-3 using 1N HCl. The organic phase was collected after solvent extraction from ethyl
acetate and dried over MgSO and in vacuo. The product was purified by silica-gel column
4
chromatography and analyzed by 1H NMR spectroscopy.
4
.6.2. 3-Phenylpropanoic acid (5a, Table 5, entry 1)
1
H NMR (400MHz, CDCl ): ): δ 11.22 (br, 1H), 7.33-7.27 (m, 2H), 7.24-7.20 (m, 3H), 2.96 (t, J =
3
7
.8 Hz, 2H), 2.69 (t, J = 7.8 Hz, 2H). CAS Number: 501-52-0.
4
.6.3. 2-Methyl-3-phenylpropanoic acid (5d, Table 5, entry 2)
1
H NMR (400MHz, CDCl ): δ 11.81 (br, 1H), 7.28 (t, J = 7.5 Hz, 2H), 7.21 (t, J = 7.1 Hz, 1H), 7.19
3
(d, J = 7.6 Hz, 2H), 3.07 (dd, J = 13.5, 6.5 Hz, 1H), 2.76 (sextet, J = 7.0 Hz, 1H), 2.66 (dd, J = 13.6,
8
.0 Hz, 1H), 1.17 (d, J = 6.5 Hz, 3H). CAS Number: 1009-67-2.
4
.6.4. 3-(2-Methylphenyl)propanoic acid (5e, Table 5, entry 3)
1
H NMR (400MHz, CDCl ): δ 10.47(br, 1H), 7.14-7.08 (m, 4H), 2.92 (t, J = 7.9 Hz, 2H), 2.61 (t, J
3
=
8.1 Hz, 2H), 2.29 (s, 3H). CAS Number: 22084-89-5.
4
.6.5. 3-(2-Hydroxyphenyl)propanoic acid (5f, Table 5, entry 4)
1
H NMR (400MHz, DMSO-d ): δ 7.04 (d, J = 7.4 Hz, 1H), 7.00 (t, J = 7.7 Hz, 1H), 6.76 (d, J = 7.8
6
1
7

ACCEPTED MANUSCRIPT
Hz, 1H), 6.69 (t, J = 7.2 Hz), 3.35 (H O), 2.73 (t, J = 7.6 Hz, 2H), 2.45 (t, J = 7.8 Hz, 2H). CAS
2
Number: 495-78-3.
4
.6.6. 3-(2-Methoxyphenyl)propanoic acid (5g, Table 5, entry 5)
1
H NMR (400MHz, DMSO-d ): δ 7.19 (td, J = 7.8, 1.6 Hz, 1H), 7.14 (dd, J = 7.5, 1.6 Hz, 1H), 6.95
6
(dd, J = 8.2, 0.9 Hz, 1H), 6.86 (td, J = 7.4, 1.4 Hz, 1H), 3.79 (s, 3H), 2.77 (t, J = 7.7 Hz, 2H), 2.46 (t, J
=
7.7 Hz, 2H). CAS Number: 6342-77-4.
4
.6.7. 4-Phenyl-2-butanone (5b, Table 6, entry 6)
1
H NMR (400MHz, CDCl ): δ 7.30-7.24 (m, 2H), 7.22-7.14 (m, 3H), 2.87 (t, J = 4.7 Hz, 2H), 2.75
3
(t, J = 4.7 Hz, 2H), 2.13 (s, 3H). CAS Number: 2550-26-7.
4
.6.8. Methyl 3-phenylpropanoate (5h, Table 5, entry 7)
1
H NMR (400MHz, CDCl ): δ 7.30-7.24 (m, 2H), 7.21-7.16 (m, 3H), 3.67 (s, 3H), 2.95 (t, J = 7.8
3
Hz, 2H), 2.64 (t, J = 7.8 Hz, 2H). CAS Number: 103-25-3.
4
.6.9. 3-Phenyl-1-propanol (5c, Table 5, entry 8)
1
H NMR (400MHz, CDCl ): δ 7.28-7.24 (m, 2 H), 7.21-7.16 (m, 3 H), 3.63 (t, J = 6.6 Hz, 2 H),
3
2
.71 (t, J = 7.7 Hz), 2.83 (br, 1 H), 1.90 (quintet, J = 7.5 Hz, 2 H). CAS Number: 122-97-4.
4
.6.10. 1,3-Diphenyl-1-propanone (5i, Table 5, entry 9)
1
H NMR (400MHz, CDCl ): δ 7.96 (d, J = 6.9 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 6.6 Hz,
3
2
H), 7.30-7.22 (m, 5H), 3.31 (t, J = 7.7 Hz, 2H), 3.07 (t, J = 7.5 Hz, 2H). CAS Number: 1083-30-3.
4
.6.11. 3-(4-Methoxyphenyl)-1-phenyl-1-propanone (5j, Table 5, entry 10)
1
H NMR(300MHz, CDCl ): δ 7.94 (d, J = 7.7 Hz, 2H), 7.54 (t, J = 6.0 Hz, 1H), 7.44 (t, J = 6.9 Hz,
3
2
H), 7.17 (d, J = 8.1 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 3.78 (s, 3H,), 3.27 (t, J = 7.7 Hz, 2 H), 3.01 (t,
J = 7.7 Hz, 2 H). CAS Number: 1669-49-4.
1
8

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4
.6.12. Recycling tests of Pd catalyst in hydrogenations.
Three kinds of hydrogenation reactions were carried out. The first eight runs were with 4-phenyl-3-
butene-2-one 4b, the 9th run was with methyl trans-cinnamate 4h and the last run was with cinnamyl
alcohol 4c. The hydrogenation reactions were performed as described above (Table 6). After the first
reaction was complete, catalyst was recovered by hot filtration and air-dried. The recovered catalyst
was successively subjected to the next runs of the coupling reaction under the same reaction
conditions as the first run.
Acknowledgments
This research was supported by the Basic Science Research Program through the National Research
Foundation of Korea (NRF), funded by the Ministry of Education (2015R1D1A1A09058536) and the
Korean Ministry of Education through the BK21-Plus Project of the Hanyang University Graduate
Program.
Appendix A. Supplementary information
Supplementary information related to this article can be found at
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•
•
•
Palladium nanoparticles supported on functionalized bidentate reverse phase silica as
heterogeneous catalysts.
Application of the catalysts to Suzuki-Miyaura reaction and Hydrogenation at room
temperature in water.
Wide reaction scope with quantitative yields, short reaction time and recyclability.
1