FULL PAPERS
DOI: 10.1002/adsc.200900270
“Click” Polymer-Supported Palladium Nanoparticles as Highly
Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling
Reactions under Ambient Conditions
Ctia Ornelas,a Abdou K. Diallo,a Jaime Ruiz,a and Didier Astruca,*
a
Institut des Sciences Molculaires, UMR CNRS N85255, Universit Bordeaux 1, 33405 Talence Cedex, France
Fax: (+ 33)-5-4000-6994; e-mail: d.astruc@ism.u-bordeaux1.fr
Received: April 17, 2009; Revised: June 30, 2009; Published online: September 8, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900270.
Abstract: Complexation of palladium(II) acetate
[PdACHTUNGRE(OAc)2] or dipotassium tetrachloropalladate
[K2PdCl4] to “click” polymers functionalized with
phenyl, ferrocenyl and sodium sulfonate groups gave
polymeric palladium(II)-triazolyl complexes that
were reduced to “click” polymer-stabilized palladium
nanoparticles (PdNPs). Transmission electron micro-
scopy (TEM) showed that reduction using sodium
borohydride (NaBH4) produced PdNPs in the 1–
3 nm range of diameters depending on the nature of
the functional group, whereas slow reduction using
methanol yielded PdNPs in the 22–25 nm range. The
most active of these PdNPs (0.01% mol Pd), stabi-
lized by poly(ferrocenyltriazolylmethyl)styrene, cata-
lyzed the hydrogenation of styrene at 25 8C and 1
Introduction
Over the last decade, metal nanoparticles (NPs) have
appeared as one of the most promising solutions to-
wards efficient catalysis under mild, environmentally
benign conditions. The stabilization of NPs for further
catalytic use has been achieved by a variety of means
including ligands, surfactants, ionic liquids, supercriti-
cal micro-emulsions, polymers and dendrimers. Catal-
ysis by polymer-supported metal nanoparticles has
been the subject of extensive studies since the 1990s
due to the great efficiency in many reactions with
mechanistic issues.[1–3] In particular, polymer-stabilized
palladium nanoparticles (PdNPs) are of special inter-
est,[4] because they are active in olefin hydrogena-
tion[4,5] and various C C coupling reactions[6] that are
usually catalyzed by palladium complexes.[3,7] In addi-
tion, it is possible to provide water-soluble as well as
organo-soluble PdNPs depending on the hydrophilici-
ty of the supporting polymers.[1,4]
Adv. Synth. Catal. 2009, 351, 2147 – 2154  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
atm hydrogen, with turnover numbers (TONs) of
200,000. When stabilized by the water-soluble poly-
ACHTUNGRE(sodium sulfonate-triazolylmethyl)styrene, the
PdNPs (0.01% mol Pd) catalyze the Suzuki–Miyaura
coupling between iodobenzene (PhI) and phenylbor-
onic acid [PhB(OH)2] in water/ethanol (H2O/EtOH)
at 25 8C with TONs of 8,200. This high catalytic ac-
tivity is comparable to that obtained with “click”
dendrimer-stabilized PdNPs under ambient condi-
tions.
Keywords: catalysis; “click” polymers; hydrogena-
tion; palladium nanoparticles; Suzuki–Miyaura reac-
tion; water-soluble catalyst
The concept of using nitrogen-based ligands present
on the dendritic backbone for encapsulation of Pd(II)
whereby, upon reduction to Pd(0), the PdNPs formed
are stabilized by the dendrimers, was pioneered by
Crooks and colleagues who have used the poly(ami-
doamine) dendrimers (PAMAM).[1a,8] Recently we
have reported that triazole-containing dendrimers,
synthesized by the “click” reaction of copper-cata-
lyzed azide/alkyne 1,3-dipolar cycloaddition
(CuAAC),[9] are able to bind Pd(II) by coordination
of their triazole ligands.[10] We have also shown that,
after reduction of the Pd(II) already incorporated in
the dendritic backbone to Pd(0), the PdNPs formed
are stabilized by the dendrimers, and that these
“click” dendrimer-encapsulated nanoparticles (DENs)
are much more stable and catalytically efficient than
those stabilized by PAMAM dendrimers.[11] The main
advantage of the DENs is that, knowing the ratio of
Pd(II) per triazole ligand, it is possible to control the
exact number of metal atoms in the NPs and there-
fore their sizes.[11]
2147
 FULL PAPERS
The aim of the present work is to investigate
whether triazole-containing polymers,[12–14] that are
more easily accessible than dendrimers, can also be
catalytically efficient and stable as the “click” DENs.
Although the functionalization of polymers using the
“click” CuAAC reaction has been extensively exploit-
ed over the last five years,[12–14] the presence of the tri-
azole heterocycles on the polymeric structures have
not been yet exploited for metal coordination purpos-
es. In this work, we have functionalized the easily ac-
cessible poly(azidomethyl)styrene with three distinct
terminal alkynes (phenylacetylene, ethynylferrocene
and sodium propargylsulfonate) using the “click”
CuAAC reaction. The three resulting triazole-con-
taining polymers were used to bind Pd(II) that, upon
reduction to Pd(0), formed the first “click” polymer-
stabilized PdNPs that are catalytically active in olefin
hydrogenation and Suzuki–Miyaura C C coupling re-
actions under mild conditions.
Scheme 1. Synthesis of the “click” polymers.
2148 asc.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Ctia Ornelas et al.
Results
Synthesis of the “Click” Polymers
Classic radical polymerization of p-chloromethylstyr-
ene, using AIBN as initiator, afforded poly(chlorome-
thyl)styrene (1) in 67% yield. The resulting poly-
ACHTUNGRE(chloromethyl)styrene was analyzed by size exclusion
chromatography (SEC) showing an average molecular
weight (MW) of 3,600 that corresponds to a degree of
polymerization (DP) of 24 and a polydispersity index
(PDI) of 1.33. The chlorides in polymer 1 were substi-
tuted by azide groups upon reaction with sodium
azide in dimethylformamide (DMF) at 80 8C for 16 h,
yielding the poly(azidomethyl)styrene 2. The comple-
tion of the azidation reaction was verified using
1
H NMR by the complete disappearance of the
CH2Cl peak at 4.53 ppm and the appearance of the
CH2N3 peak at 4.27 ppm.
Three polymers containing triazole ligands were
synthesized by “click” reaction[9] between the azido
groups of polymer 2 and phenylacetylene, ethynylfer-
rocene and sodium propargylsulfonate, using copper
sulfate/sodium ascorbate in THF/water (1:1)
(Scheme 1). The completion of the “click” reactions
Adv. Synth. Catal. 2009, 351, 2147 – 2154
“Click” Polymer-Supported Palladium Nanoparticles as Highly Efficient Catalysts
was verified using 1H NMR by the total disappear-
ance of the CH2N3 peak at 4.27 ppm as well as by in-
frared spectroscopy (IR) by complete disappearance
of the N3 band at 2090 cm 1. The resulting polymers
poly(phenyltriazolylmethyl)styrene (3), poly(ferro-
ACHTUNGREcenyltriazolyl-methyl)styrene (4) and poly(sodium sul-
fonate-triazolylmethyl)styrene (5) were characterized
by 1H and 13C NMR, elemental analysis and SEC, and
they all disclosed a degree of polymerization of ap-
proximately 24 and a PDI of 1.33, showing that the
azidation as well as the CuAAC reaction did not
change the polymer backbone. Polymers 3 and 4 are
soluble in most common organic solvents such as
methylene chloride, chloroform and tetrahydrofuran,
whereas polymer 5 is soluble in aqueous media due to
the presence of the sodium sulfonate groups.
Complexation of Pd(II) and Characterization of the
PdNPs Stabilized by the “Click” Polymers
In our previous reports, we showed that triazole het-
erocycles can complex Pd(II), the ratio of triazole
ring per palladium atom being dependent on the type
of palladium precursor complex.[10] We also showed
that, in organic solvents in presence of methanol, tri-
ACHTUNGREazole ligands coordinate to PdACHTUNGRE(OAc)2 in a Pd:triazole
ring ratio of 1:1,[11c] and in aqueous media the triazole
ligands also coordinate to K2PdCl4 in a Pd:triazole
ring 1:1 ratio.[11d] This ratio is now applied to the
“click” polymers in order to introduce Pd(II) into the
polymers that, after reduction, would afford polymer-
stabilized-PdNPs.
For polymers 4 and 5, the polymer-stabilized-NPs
were synthesized in CHCl3/MeOH (2:1) by adding
one equivalent of PdACHTUNGRE(OAc)2 per triazole unit (since
the click reactions were complete, the mass of poly-
mer was divided by the molecular weight of the mon-
omeric unit, in order to calculate the amount of palla-
dium complex to be added). The reduction of Pd(II)
to Pd(0) in polymers 4 and 5 was performed either by
stirring in the presence of methanol for 16 h or by
adding 10 equivalents of NaBH4, in order to compare
the influence of the reducing agents on the NP size
and catalytic activity. For polymer 5, the polymer-sta-
bilized NPs were synthesized in aqueous solution by
addition of one equivalent of K2PdCl4 per triazole
unit, followed by addition of 10 equivalents of
NaBH4. After complexation of Pd(II) [PdACHTUNGRE(OAc)2 or
K2PdCl4] to the triazole ligands of the polymers fol-
lowed by reduction to Pd(0), all the polymer-stabi-
lized NPs were characterized by transmission electron
microscopy (TEM). The TEM data are gathered in
Table 1. Figure 1 and Figure 2 show the TEM pictures
and size-distribution histograms of the PdNPs stabi-
lized by polymer 4 subsequent to reduction using
methanol and the PdNPs stabilized by polymer 5 sub-
Adv. Synth. Catal. 2009, 351, 2147 – 2154  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPERS
Table 1. Diameters of the PdNPs stabilized by the “click”
polymers, obtained by TEM.
PdNPs Reducing agent Diameter [nm]
PdNPs stabilized by 3 NaBH4 1.0  0.2
PdNPs stabilized by 3 MeOH 25.2  6.0
PdNPs stabilized by 4 NaBH4 1.7  0.4
PdNPs stabilized by 4 MeOH 22.4  4.7
PdNPs stabilized by 5 NaBH4 2.8  0.4
sequent to reduction using NaBH4, respectively (see
Supporting Information for all the other TEM images
and histograms).
The TEM data show that the PdNPs obtained by
reduction with NaBH4 are much smaller (1–3 nm
range) than those obtained by reduction with metha-
nol (22–25 nm range). This result is in accordance
with the tendency found for polymer-stabilized
PdNPs already reported.[2,3] For the polymer-stabilized
PdNPs, the size of the NPs is determined by the metal
reduction rate (the reduction with methanol is much
slower than that using NaBH4) in contrast to the den-
drimer-stabilized PdNPs in which the size is governed
by the number of Pd(II)-triazole units in the dendri-
mer.[11]
Catalytic Efficiency of the “Click” Polymer-Stabilized
PdNPs in the Hydrogenation and Suzuki–Miyaura
Reactions
The “click” polymer-stabilized PdNPs described
above were tested as catalysts in hydrogenation of
styrene to ethylbenzene and Suzuki–Miyaura coupling
between PhI and PhB(OH)2, in order to investigate
their catalytic efficiency and stability and eventually
to compare them with the “click” DENs reported ear-
lier.[11] The amount of catalyst used in both reactions
was 0.01% mol Pd, and the results obtained for the
hydrogenation and Suzuki–Miyaura reactions are
gathered in Table 2 and Table 3, respectively. The re-
actions were followed by GC, and the turnover fre-
quency values (TOF) were determined on the basis of
the yield of formation of final product per hour and
are expressed in mol substrate (mol Pd) 1 h 1. The
turnover number values (TON) express the total
amount of substrate catalyzed before degradation and
are expressed in mol substrate/mol Pd (in the case of
the hydrogenation reactions, the substrate was added
several times until complete degradation of the cata-
lyst).
Table 2 shows that the PdNPs, stabilized by poly-
mer 3 and soluble in organic solvents, and those stabi-
lized by polymer 4 have comparable activities, but the
latter are much more stable than the former, perform-
asc.wiley-vch.de 2149
 FULL PAPERS Ctia Ornelas et al.

Figure 1. PdNPs stabilized by polymer 4 using methanol as the reducing agent: a) TEM image and b) size-distribution histo-
gram.

Figure 2. PdNPs stabilized by polymer 5 using NaBH4 as the reducing agent: a) TEM image and b) size-distribution histo-
gram.

Table 2. Catalytic efficiencies (TOF) and stabilities (TON) Discussion

obtained for all the new catalysts for styrene hydrogenation
at 0.01% mol Pd, 25 8C and 1 atm H2. In the present work, it was anticipated that the advan-
Catalyst Reducing agent TOF [a]
TON [b] tages disclosed in the strategy utilizing the “click”
dendrimer-stabilized PdNPs would still be beneficial,
PdNPs stabilized by 3 NaBH4 1,100 26,000 at least to a certain extent, for catalysis with “click”
PdNPs stabilized by 3 MeOH 1,400 17,000 polymer-stabilized PdNPs. Even if the “click” poly-
PdNPs stabilized by 4 NaBH4 930 200,000 mers, contrary to dendrimers, do not allow the precise
PdNPs stabilized by 4 MeOH 1,740 150,000
control over the NP size, the results show that the
[a]
The catalytic activity of the PdNPs was investigated for “click” polymer-stabilized PdNPs present a catalytic
the hydrogenation of styrene at 0.01% mol Pd, in CHCl3/ efficiency of the same order as that disclosed earlier
MeOH (2:1), 25 8C and 1 atm H2. The reactions were fol- for the “click” dendrimer-stabilized PdNPs. In the
lowed by GC, and the TOF values were determined on present study, two extremely different PdNP sizes
the basis of the yield of ethylbenzene per hour and are were obtained by variation of the nature of the reduc-
expressed in mol H2 (mol Pd) 1 h 1. tant (NaBH4 vs. methanol). As expected, the PdNPs
[b]
The TONs are expressed in mol substrate/mol Pd.
obtained using NaBH4 are much smaller than those
using methanol because the stronger reductant
(NaBH4) produces the smaller PdNPs.[15] While the
ing up to 200,000 catalytic cycles (mol substrate/mol relation between the strength of the reducing agent
Pd) for styrene hydrogenation at 25 8C. and the NP size is easy to understand, the comparison
Table 3 shows that the water-soluble PdNPs stabi- between the catalytic efficiency of the various NPs is
lized by polymer 5 are the most active PdNPs in the not straightforward. It is expected that smaller NPs
Suzuki–Miyaura coupling between iodobenzene and would be much more active (per mol Pd) than larger
phenylboronic acid, presenting a catalytic efficiency NPs. Our results, however, show that the larger
of 900 mol PhI (mol Pd) 1 h 1 and a yield of 82% PdNPs are more active than the smaller ones. This is
after 24 h at 25 8C (TON = 8,200). probably due to the difference of nature of the PdNP

2150 asc.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Synth. Catal. 2009, 351, 2147 – 2154
“Click” Polymer-Supported Palladium Nanoparticles as Highly Efficient Catalysts FULL PAPERS

Table 3. Catalytic efficiencies (TOF) and stabilities (TON) obtained for all the new catalysts for the Suzuki–Miyaura cou-
pling between PhB(OH)2 and PhI at 0.01% mol Pd and 25 8C.

Catalyst Reducing agent Time (Yield) Time (Yield) Time (Yield) TOF[c] TON[d]
PdNPs stabilized by 3[a] NaBH4 24 h (14%) 48 h (15%) – 60 1,500
PdNPs stabilized by 3[a] MeOH 24 h (32%) 48 h (41%) 72 h (44%) 130 4,400
PdNPs stabilized by 4[a] NaBH4 24 h (14%) 48 h (15%) – 60 1,500
PdNPs stabilized by 4[a] MeOH 24 h (32%) 48 h (41%) 72 h (44%) 130 4,400
PdNPs stabilized by 5[b] NaBH4 7 h (62%) 24 h (82%) – 900 8,200
[a]
The PdNPs were formed using PdACHTUNGRE(OAc)2, and the catalytic reactions were performed in CHCl3/MeOH (2:1), at 0.01%
mol Pd, 25 8C.
[b]
The PdNPs were formed using K2PdCl4, and the catalytic reactions were performed in H2O/EtOH (1:1) at 0.01% mol Pd,
25 8C.
[c]
The reactions were followed by GC, and the TOF values were determined on the basis of the yield of formation of bi-
phenyl. The TOFs are expressed in mol PhI (mol Pd) 1 h 1.
[d]
The TONs are expressed in mol substrate/mol Pd.

surfaces that result from the different reducing agents Conclusions

used. In particular the borates, that were formed
when NaBH4 was used, are not formed along the
methanol reduction. On the one hand, the PdNPs
produced by reduction with NaBH4 are smaller,
which should have made them more efficient, but on
the other hand the borates formed at their surface
probably reduce their catalytic activity.
For styrene hydrogenation, the PdNPs stabilized by
polymer 4 and soluble in organic solvents are much
more stable (the TON reaching values of 200,000 mol
H2 {mol Pd} 1) than those stabilized by polymer 3
(TON values are approximately eight times higher for
the former catalyst than for the latter one). It is prob-
able that this higher stability obtained for NPs that
are stabilized by polymer 4 is due to the tri-dimen-
sional bulk of the ferrocenyl groups acting as steric
protectors of the metal NPs (without coordination to
the PdNP surface that would decrease the activity).
On the other hand, there is no significant difference
on the catalytic activity of the NPs stabilized by poly-
mers 3 and 4 in the Suzuki–Miyaura coupling, proba-
bly due to the nature of the leaching mechanism (that
is typical of this type of reaction when catalyzed by
PdNPs).[3,11] Note that the Suzuki–Miyaura coupling
reaction was successfully performed in aqueous media
(at 0.01% mol Pd, at 25 8C) using the water-soluble
PdNPs stabilized by polymer 5, reaching 82% yield in
24 h. The fact that the best overall results for the
Suzuki–Miyaura coupling are obtained with the
water-soluble “click” polymer-stabilized NPs in aque-
ous solvent using K2PdCl4 as a source of Pd(II) and
NaBH4 as a reducing agent indicates that the borates
formed do not significantly inhibit the PdNP surface,
probably due to their hydrolysis in the aqueous sol-
vent.
Coordination of Pd(II) by triazole-containing poly-
mers, followed by reduction to Pd(0) using either
NaBH4 or methanol, yields small (1–3 nm) or, respec-
tively, large (21–24 nm) “click” polymer-stabilized
PdNPs that are soluble in organic solvents or in water
depending on the functional group of the terminal
alkyne used in the “click” reaction. The three new
“click” polymer-stabilized PdNPs are active catalysts
for styrene hydrogenation and Suzuki–Miyaura reac-
tions at 25 8C using 0.01% mol Pd. For styrene hydro-
genation, the most active among these PdNP catalysts
are those stabilized with “click” polymers containing
ferrocenyl groups on the side chain in which the
Pd(II) was reduced to Pd(0) using methanol (styrene
hydrogenation at 1 atm H2 with TON up to 200,000).
For the Suzuki–Miyaura reaction, the most active cat-
alyst is the one for which the PdNPs are stabilized by
“click” polymers containing sodium sulfonate groups
on the side chain providing water solubility [82%
yield in 24 h, TOF = 880 mol PhI (mol Pd) 1 h 1 and
TON = 8,200].
These new “click” polymer-stabilized PdNPs show
a high catalytic activity under ambient conditions that
is comparable to that of the “click” dendrimer-stabi-
lized PdNPs. The remaining challenge is extension of
this type of catalysts Suzuki–Miyaura coupling with
aryl chlorides for which some molecular Pd-phos-
phine catalysts are very efficient.[7]
Experimental Section
General Data
Ethynylferrocene, phenylacetylene, and all the olefinic sub-
strates were purchased from Sigma–Aldrich. Sodium prop-
argyl sulfonate was synthesized according to ref.[16] Synthe-

Adv. Synth. Catal. 2009, 351, 2147 – 2154  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim asc.wiley-vch.de 2151
 FULL PAPERS
ses of the PdNPs were carried out using Schlenk techniques
using degassed solvents.
Synthesis of Poly(chloromethyl)styrene, Polymer 1
p-Chloromethylstyrene (2.17 g, 14.2 mmol) was dissolved in
60 mL of dry toluene and heated to 80 8C. AIBN (0.116 g,
0.701 mmol) was added to the solution, and the reaction
mixture was allowed to stir at 80 8C for 48 h. Toluene was re-
moved under vacuum, and the crude product was washed
with methanol and precipitated twice with dichloromethane/
methanol. The polymer poly(chloromethylstyrene) was ob-
tained as a white powder; yield: 1.44 g (67%). 1H NMR
(CDCl3, 300 MHz): d = 7.06 and 6.49 (arom. CH of styrenic
ring), 4.53 (CH2Cl), 1.67 and 1.39 (CH and CH2 of polymer
chain); 13C NMR (CDCl3, 75 MHz): d = 138.8 and 135.5
(arom. Cq), 127.0 and 126.6 (arom. CH of styrenic ring), 51.5
(CH2Cl), 43.1 and 41.3 (CH and CH2 of polymer chain).
SEC data: MW: 3600 g·mol 1; PDI: 1.33; DP: 24.
Synthesis of Poly(azidomethyl)styrene, Polymer 2
Polymer 1 (0.700 g) was dissolved in 30 mL of dry DMF,
NaN3 (0.90 g, 14.0 mmol) was added, and the reaction mix-
ture was heated at 80 8C for 16 h. The solvent was removed
under vacuum, and the product was dissolved in dichloro-
methane and washed with water. The organic layer was
dried with sodium sulfate, filtered, and the solvent was re-
moved. Polymer 2 was obtained as a white waxy product;
yield: 0.645 g (91%). 1H NMR (CDCl3, 300 MHz), d = 7.01
and 6.51 (arom. CH of styrenic ring), 4.27 (CH2N3), 1.72 and
1.45 (CH and CH2 of polymer chain); 13C NMR (CDCl3,
75 MHz), d = 144.3 and 132.1 (arom. Cq), 127.8 and 127.4
(arom. CH of styrenic ring), 53.9 (CH2Cl), 39.7 (CH and
CH2 of polymer chain).
Synthesis of Poly(phenyltriazolylmethyl)styrene,
Polymer 3
Polymer 2 (0.165 g) and phenylacetylene (0.5 mL) were dis-
solved in 60 mL of tetrahydrofuran (THF) and 60 mL of
water were added (1:1 THF/water). At 0 8C, CuSO4·5 H2O
was added (0.347 g, 1.39 mmol; 1 M aqueous solution) fol-
lowed by dropwise addition of a freshly prepared solution of
sodium ascorbate (0.551 g, 2.78 mmol; 1 M aqueous solu-
tion). The solution was allowed to stir for 16 h at room tem-
perature. After removing THF under vacuum, dichlorome-
thane and an aqueous solution of ammonia were added. The
mixture was allowed to stir for 10 min, in order to remove
the copper trapped inside the polymer. The organic phase
was washed twice with water, dried with sodium sulfate, fil-
tered, and the solvent was removed under vacuum. The
product was washed with pentane in order to remove the
excess of alkyne and precipitated twice using dichlorome-
thane/pentane. Polymer 3 was obtained as a white powder;
yield: 0.237 g (65%). 1H NMR (CDCl3, 300 MHz): d = 8.02
(CH of triazole), 7.79 and 7.30 (CH of phenyl ring), 6.79
and 6.31 (arom. CH of styrenic ring), 5.36 (CH2-triazole),
1.72 and 1.53 (CH and CH2 of polymer chain); 13C NMR
(CDCl3, 75 MHz): d = 147.9 (Cq of triazole), 132.9–125.8
(aromatics), 120.9 (CH of triazole), 53.7 (CH2-triazole), 41.3
(CH and CH2 of polymer chain); SEC data: MW:
2152 asc.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Ctia Ornelas et al.
6300 g·mol 1; PDI: 1.33; DP: 24; anal. calcd. for [C17H15N3]n :
C 78.13, H 5.79; found: C 77.35, H 6.12.
Synthesis of Poly(ferrocenyltriazolylmethyl)styrene,
Polymer 4
Polymer 2 (0.115 g) and ethynylferrocene (0.335 g,
1.60 mmol) were dissolved in 60 mL of tetrahydrofuran
(THF), and 60 mL of water weere added (1:1 THF/water).
At 0 8C, CuSO4·5 H2O was added (0.265 g, 1.06 mmol; 1 M
aqueous solution) followed by dropwise addition of a freshly
prepared solution of sodium ascorbate (0.420 g, 2.12 mmol;
1 M aqueous solution). The solution was allowed to stir for
16 h at room temperature. After removing THF under
vacuum, dichloromethane and an aqueous solution of am-
monia were added. The mixture was allowed to stir for
10 min in order to remove the copper trapped inside the po-
lymer. The organic phase was washed twice with water,
dried with sodium sulfate, filtered through paper, and the
solvent was removed under vacuum. The product was
washed with pentane in order to remove the excess of
alkyne and precipitated twice using dichloromethane/pen-
tane. The poly(p-ferrocenyltriazolylmethylstyrene) was ob-
tained as an orange waxy product; yield: 0.233 g (69%).
1
H NMR (CDCl3, 300 MHz): d = 7.73 (CH of triazole), 6.73
and 6.24 (arom. CH of styrenic ring), 5.37 (CH2-triazole),
4.78, 4.30 and 4.07 (CH of ferrocenyl group), 1.36 (CH and
CH2 of polymer chain); 13C NMR (CDCl3, 75 MHz): d =
146.4 (Cq of triazole), 132.4–127.5 (aromatics), 119.4 (CH of
triazole), 75.1, 69.2, 68.3 and 66.2 (CH and Cq of ferrocenyl
group), 52.9 (CH2-triazole), 41.3 (CH and CH2 of polymer
chain); SEC data: MW: 9000 g·mol 1; PDI: 1.33; DP:24;
anal. calcd. for [C21H19N3Fe]n : C 68.31, H 5.19; found: C
67.80, H 5.45.
Synthesis of Poly(sodium sulfonate-
triazolylmethyl)styrene, Polymer 5
The poly(azidomethylstyrene) polymer (0.200 g) was dis-
solved in 30 mL of tetrahydrofuran (THF), and 20 mL of an
aqueous solution of sodium propargylsulfonate (0.395 g,
2.78 mmol) were added. At 0 8C, CuSO4 (0.462 g, 1.85 mmol;
1 M aqueous solution) was added, followed by the dropwise
addition of a freshly prepared solution of sodium ascorbate
(0.733 g, 3.70 mmol, 1 M aqueous solution). Water was
added in order to obtain a solution in 1:1 THF/H2O. The so-
lution was allowed to stir for 16 h at room temperature.
After removing THF under vacuum, the polymer remained
dissolved in the aqueous solution. The polymer was purified
by dialysis against 1 L of aqueous ammonia solution for
three days [in order to remove Cu(I) that remains trapped
inside the polymer] and against 1 L water for one day (the
dialysis solutions were substituted twice a day). After re-
moving water, the polymer poly(sodium sulfonatetriazolyl-
methylstyrene) was obtained as a light yellow waxy product;
yield: 0.100 g (30%). 1H NMR (D2O, 300 MHz): d = 7.83
(CH of triazole), 7.10–6.90 (arom. CH of styrenic ring), 4.2
(CH2SO3Na), 1.20–0.70 (CH and CH2 of polymer chain);
SEC data: MW: 8000 g·mol 1; PDI: 1.33; DP: 28.
Adv. Synth. Catal. 2009, 351, 2147 – 2154
“Click” Polymer-Supported Palladium Nanoparticles as Highly Efficient Catalysts
Transmission Electron Microscopy (TEM)
4
Samples were prepared by setting a drop of a 4  10 M so-
lution of PdNPs (concentration in mol Pd) on a holey-
carbon-coated Cu TEM grid. The size of the PdNPs was
measured using the software sigmascanpro (for each sample,
about 100 nanoparticles were measured).
Gas Chromatography (GC)
GC data were recorded on a Hewlett Packard 5890 Series II
gas chromatograph, equipped with a flame ionization detec-
tor. Helium was used as the carrier gas for all the substrates.
The injector and detector temperatures were 240 8C.
General Procedure for the Preparation of the PdNPs
For PdNPs stabilized by polymers 3 or 4, the nanoparticles
were synthesized in CHCl3/MeOH (2:1) using 1 equiv. of
PdACHTUNGRE(OAc)2 per triazole unit. For PdNPs stabilized by polymer
5, the nanoparticles were synthesized in water using 1 equiv.
K2PdCl4 per triazole unit.
1 mL of solution of “click” polymer (1 mg) was intro-
duced in a Schlenk flask. 1 mL of a solution containing
1 equiv. of PdACHTUNGRE(OAc)2 (in CHCl3) or K2PdCl4 (in water) per
triazole unit was added. Then NaBH4 (10 equiv. per Pd) was
added, and the light-yellow solution turned to black indicat-
ing nanoparticle formation. For the nanoparticles formed by
methanol reduction, no NaBH4 was added allowing the
yellow CHCl3/MeOH solution containing the polymer-Pd
complexes to stir for 16 h, under a nitrogen atmosphere, re-
sulting in a dark-brown solution.
Hydrogenation Reactions
The PdNPs were freshly prepared in a Schlenk flask, and
10,000 equiv. of substrate (per mol Pd) was added. The
Schlenk flask was filled with H2 (1 atm), and the solution
was allowed to stir at 25 8C. For re-use of the catalyst, the
substrate was added to the reaction solution until catalyst
degradation. Calculation of the turnover frequency (TOF)
was carried out using several samples of the solution that
were extracted at different reaction times and analyzed by
GC. Calculation of the turnover number (TON) was carried
out using the sum of substrate that reacted in all the catalyt-
ic cycles, after analyzing the final reaction solution (after
catalyst degradation).
Suzuki–Miyaura Reactions
The PdNPs were freshly prepared in a Schlenk flask and
K3PO4, phenylboronic acid and iodobenzene were succes-
sively added. The solution was allowed to stir under N2 at
25 8C.
For the reactions performed in organic solvents, the reac-
tants (iodobenzene and phenylboronic acid and final prod-
uct (biphenyl) were soluble in the reaction media, so the re-
action kinetics was followed by simply taking several ali-
quots of the reaction solutions and analyzing by GC.
In the case of the reaction performed in H2O/EtOH, the
reactants (iodobenzene and phenylboronic acid were soluble
in the reaction media, but the final product (biphenyl) was
not, precipitating as a white solid. In this case, the catalytic
reaction was performed in several Schlenk flasks in parallel.
Adv. Synth. Catal. 2009, 351, 2147 – 2154  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPERS
The PdNPs were prepared in one Schlenk and then divided
in several Schlenk flasks containing the reactants for the
Suzuki–Miyaura reaction. At given times, one reaction solu-
tion was extracted with dichloromethane (all reactants and
final product are soluble) and analyzed by GC.
Supporting Information Available
TEM and size distribution histograms of all the click-poly-
mer-stabilized PdNPs.
Acknowledgements
We are grateful to Dr. Eric Cloutet (LCPO, Bordeaux) for
helpful assistance in the SEC experiments, and to Fundażo
para a CiÞncia e a Tecnologia (FCT), Portugal (Ph. D. grant
to CO), the Institut Universitaire de France (IUF, DA), the
CNRS, the ANR (CATAQ project) and the Universit Bor-
deaux I for financial support.
References
[1] a) Y. Niu, R. M. Crooks, C. R. Chim. 2003, 6, 1049;
b) M-C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293;
c) D. Astruc, F. Lu, J. Ruiz, Angew. Chem. 2005, 117,
8062; Angew. Chem. Int. Ed. 2005, 44, 7852; d) J. G.
De Vries, Dalton Trans. 2006, 421; e) Nanocatalysis
(Eds.: U. Heiz, U. Landman), Springer, Berlin, 2007;
f) D. Astruc, Inorg. Chem. 2007, 46, 1884; g) Nanoparti-
cles and Catalysis, (Ed.: D. Astruc), Wiley-VCH, Wein-
heim, 2008.
[2] a) H. Bçnnemann, W. Brijoux, in: Active Metals, (Ed.:
A. Frstner), VCH, Weinheim, 1996, p 339; b) M. T.
Reetz, W. Helbig, S. A. Quaiser, in: Active Metals,
(Ed.: A. Frstner), VCH, Weinheim, 1996, p 279; c) N.
Toshima, Y. Yonezawa, New J. Chem. 1998, 22, 1179;
d) B. F. G. Johnson, Coord. Chem. Rev. 1999, 190, 1269;
e) A. Roucoux, J. Schulz, H. Patin, Chem. Rev. 2002,
102, 3757; f) S. Mandal, P. R. Selvakannan, D. Roy,
R. V. Chaudhari, M. Sastry, Chem. Commun. 2002,
3002; g) J. Dupont, G. S. Fonseca, A. P. Umpierre,
P. F. P. Fichner, J. Am. Chem. Soc. 2002, 124, 4228;
h) H. Ohde, C. M. Wai, J. Kim, M. Ohde, J. Am. Chem.
Soc. 2002, 124, 4540; i) A. Roucoux, J. Schulz, H. Patin,
Adv. Synth. Catal. 2003, 345, 222.
[3] N. T. S. Phan, M. Van der Sluys, C. J. Jones, Adv. Synth.
Catal. 2006, 348, 609.
[4] a) N. Toshima, K. Kushihashi, T. Yonezawa, H. Hirai,
Chem. Lett. 1989, 1769; b) M. V. Seregina, L. M. Bron-
stein, O. A. Platonova, D. M. Chernyshov, P. M. Valet-
sky, Chem. Mater. 1997, 9, 923; c) B. P. S. Chauhan, J. S.
Rathore, T. Bandoo, J. Am. Chem. Soc. 2004, 126,
8493; d) book on hydrogenation: The Handbook of
Homogeneous Hydrogenation, (Eds.: J. G. de Vries,
C. J. Elsevier), Wiley-VCH, Weinheim, 2006.
[5] Hydrogenation reaction using polymer-stabilized
PdNPs: a) H. Hirai, J. Macromol. Sci. Chem. 1979, 13,
633; b) N. Toshima, K. Kushihashi, T. Yonezawa, H.
Hirai, Chem. Lett. 1989, 1769; c) M. V. Seregina, L. M.
Bronstein, O. A. Platonova, D. M. Chernyshov, P. M.
asc.wiley-vch.de 2153
 FULL PAPERS
Valetsky, Chem. Mater. 1997, 9, 923; d) B. P. S. Chau-
han, J. S. Rathore, T. Bandoo, J. Am. Chem. Soc. 2004,
126, 8493.
[6] a) Y. Li, X. M. Hong, D. M. Collard, M. A. El-Sayed,
Org. Lett. 2000, 15, 2384; b) V. Kogan, Z. Aizenshtat,
R. Popovitz-Biro, R. Neumann, Org. Lett. 2002, 4,
3529; c) R. Narayanan, M. A. El-Sayed, J. Am. Chem.
Soc. 2003, 125, 8340; d) H. Oyamada, R. Akiyama, H.
Hagio, T. Naito, S. Kobayashi, Chem. Commun. 2006,
4297; e) D. Saha, K. Chattopadhyay, B. C. Ranu, Tetra-
hedron Lett. 2008, 49, 1003; f) H.-B. Pan, C-H. Yen, B.
Yoon, M. Sato, C. M. Wai, Synth. Commun. 2006, 36,
3473; g) K. C. Jin, R. Najman, T. W. Dean, O. Ishihara,
C. Muller, M. Bradley, J. Am. Chem. Soc. 2006, 128,
6276; h) L. Z. Ren, L. J. Meng, Express Polym. Lett.
2008, 2, 251; i) X. Yang, Z. Fei, D. Zhao, W. H. Ang, Y.
Li, P. J. Dyson, Inorg. Chem. 2008, 47, 3292; j) J. Du-
trand, E. Teuma, F Malbosc, Y. Kihn, M. Gomez,
Catal. Commun. 2008, 9, 273.
[7] a) J. Louie, J. F. Hartwig, Angew. Chem. 1996, 108,
2531; Angew. Chem. Int. Ed. Engl. 1996, 35, 2359;
b) W. A. Herrmann, V. P. W. Bçlm, C. P. Reisinger, J.
Organomet. Chem. 1999, 576, 23; c) C. Amatore, A.
Jutand, Acc. Chem. Res. 2000, 33, 314; d) I. P. Belet-
skaya, A. V. Cheprakov, J. Organomet. Chem. 2004,
689, 4055; e) R. B. Bedford, C. S. J. Cazin, D. Holder,
Coord. Chem. Rev. 2004, 248, 2283; f) F. Alonso, I. P.
Beletskaya, M. Yus, Tetrahedron 2005, 61, 11771.
[8] a) M. Zhao, R. M. Crooks, Angew. Chem. 1999, 111,
375; Angew. Chem. Int. Ed. 1999, 38, 364; b) R. M.
Crooks, M. Zhao, L. Sun, V. Chechik, L. K. Yeung,
Acc. Chem. Res. 2001, 34, 181; c) Y. Niu, L. K. Yeung,
R. M. Crooks, J. Am. Chem. Soc. 2001, 123, 6840;
d) L. K. Yeung, R. M. Crooks, Nano Lett. 2001, 1, 14;
e) Y. Niu, R. M. Crooks, Chem. Mater. 2003, 15, 3463;
f) R. W. J. Scott, O. M. Wilson, A.-K. Oh, E. A. Kenik,
R. M. Crooks, J. Am. Chem. Soc. 2004, 126, 15583;
g) S.-K. Oh, Y. Niu, R. M. Crooks, Langmuir 2005, 21,
10209; h) O. M. Wilson, M. R. Knecht, J. C. Garcia-
Martinez, R. M. Crooks, J. Am. Chem. Soc. 2006, 128,
4510.
[9] a) H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew.
Chem. 2001, 113, 2056; Angew. Chem. Int. Ed. 2001, 40,
2004; b) V. V. Rostovsev, L. G. Green, V. V. Fokin,
K. B. Sharpless, Angew. Chem. 2002, 114, 2708; Angew.
2154 asc.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Ctia Ornelas et al.
Chem. Int. Ed. 2002, 41, 2596; c) C. W. Tornoe, C.
Christensen, M. Medal, J. Org. Chem. 2002, 67, 3057;
d) P. Wu, A. K. Feldman, A. K. Nugent, C. J. Hawker,
A. Scheel, B. Voit, J. Pyun, J. M. J. Frchet, K. B.
Sharpless, V. V. Fokin, Angew. Chem. 2004, 116, 4018;
Angew. Chem. Int. Ed. 2004, 43, 3928; e) V. D. Bock,
H. Hiemstra, J. H. van Maarseveen, Eur. J. Org. Chem.
2006, 51.
[10] C. Ornelas, J. Ruiz, E. Cloutet, S. Alves, D. Astruc,
Angew. Chem. 2007, 119, 890; Angew. Chem. Int. Ed.
Angew. Chem. Int. Ed. Engl. 2007, 46, 872.
[11] a) C. Ornelas, L. Salmon, J. R. Aranzaes, Chem.
Commun. 2007, 4946; b) A. K. Diallo, C. Ornelas, L.
Salmon, J. Ruiz, D. Astruc, Angew. Chem. 2007, 119,
8798; Angew. Chem. Int. Ed. Engl. 2007, 46, 8644; c) C.
Ornelas, L. Salmon, J. Ruiz, D. Astruc, Chem. Eur. J.
2008, 14, 50; d) C. Ornelas, J. Ruiz, L. Salmon, D.
Astruc, Adv. Synth. Catal. 2008, 350, 837.
[12] First report on “click” polymers synthesis: B. Helms,
J. L. Mynar, C. J. Hawker, J. M. J. Frchet, J. Am.
Chem. Soc. 2004, 126, 15020.
[13] Recent reviews on “click” polymers : a) M. Meldal,
Macromol. Rapid Commun. 2008, 29, 1016; b) W. H.
Binder, R. Sachsenhofer, Macromol. Rapid Commun.
2008, 29, 952; c) P. Lundberg, C. J. Hawker, A. Hult,
M. Malkoch, Macromol. Rapid Commun. 2008, 29, 998;
d) B. Le Droumaguet, K. Velonia, Macromol. Rapid
Commun. 2008, 29, 1073; e) J. A. Johnson, M. G. Finn,
J. T. Koberstein, N. J. Turro, Macromol. Rapid
Commun. 2008, 29, 1421.
[14] a) G. K. Such, J. F. Quinn, A. Quinn, E. Tjipto, F.
Caruso, J. Am. Chem. Soc. 2006, 128, 9318; b) S. Srini-
vasachari, Y. Liu, L. E. Prevette, T. M. Reineke, Bio-
materials 2007, 28, 2885; c) D. Daz, J. J. Marrero Tella-
doa, D. Garca Velzqueza, . Gutirrez Raveloa, Tet-
rahedron Lett. 2008, 49, 1340; d) L. Campos, K. Killops,
R. Sakai, J. M. J. Paulusse, D. Damiron, E. Drocken-
mller, B. W. Messmore, C. J. Hawker, Macromolecules
2008, 41, 7063; e) E. Boisselier, A. Chan Kam Shun, J.
Ruiz, E. Cloutet, C. Belin, D. Astruc, New J. Chem.
2009, 33, 246; f) K. Itomi, S. Kobayashi, K. Morino, H.
Iida1, E. Yashima, Polym. J. 2009, 41, 108.
[15] M. Reetz, in: Nanoparticles and Catalysis, (Ed.: D.
Astruc), Wiley-VCH, Weinheim, 2008, Chap. 8, p 253.
[16] E.-H. Riu, Y. Zhao, Org. Lett. 2005, ##7##6, 1035.
Adv. Synth. Catal. 2009, 351, 2147 – 2154