Ligandless C-C bond formation via Suzuki-Miyaura reaction in micelles or water-ethanol solution using PdPtZn and PdZn nanoparticle thin films

Article abstract of DOI:10.1002/aoc.3318

PdPtZn and PdZn nanoparticle (NP) thin films were synthesized by the reduction of [PdCl₂(cod)], [PtCl₂(cod)] (cod = cis,cis-1,5-cyclooctadiene) and [Zn(acac)₂] (acac = acetylacetonate) complexes at an oil-water interface. The structure and morphology of the as-prepared NPs were characterized with X-ray diffraction, transmission electron microscopy and energy dispersive analysis of X-rays. Catalytic activity of the prepared NPs was investigated in the Suzuki-Miyaura cross-coupling reaction in H₂O-EtOH and various micellar media systems such as cetyltrimethylammonium bromide (cationic surfactant), sodium dodecylsulfate (anionic surfactant) and Pluronic P123 (non-ionic surfactant). PdPtZn and PdZn thin films exhibited higher catalytic activity compared to Pd thin film in the Suzuki-Miyaura coupling reaction due to the appropriate interaction between palladium, platinum and zinc metals. PdPtZn and PdZn nanoparticle thin films were synthesized by the reduction of [PdCl₂(cod)], [PtCl₂(cod)] and [Zn(acac)₂] complexes at an oil-water interface. Catalytic activity of the nanoparticles was investigated in Suzuki-Miyaura cross-coupling reactions in various micellar systems or water-ethanol solution.

Full text of DOI:10.1002/aoc.3318

Full paper
Received: 1 February 2015
Revised: 11 March 2015
Accepted: 16 March 2015
Published online in Wiley Online Library: 26 May 2015
(wileyonlinelibrary.com) DOI 10.1002/aoc.3318
Ligandless C–C bond formation via Suzuki–
Miyaura reaction in micelles or water–ethanol
solution using PdPtZn and PdZn nanoparticle
thin films
S. Jafar Hoseini*, Atiyeh Zarei and Hajar Rafatbakhsh Iran
PdPtZn and PdZn nanoparticle (NP) thin films were synthesized by the reduction of [PdCl2(cod)], [PtCl2(cod)] (cod = cis,cis-1,5-
cyclooctadiene) and [Zn(acac)2] (acac = acetylacetonate) complexes at an oil–water interface. The structure and morphology of
the as-prepared NPs were characterized with X-ray diffraction, transmission electron microscopy and energy dispersive analysis
of X-rays. Catalytic activity of the prepared NPs was investigated in the Suzuki–Miyaura cross-coupling reaction in H2O–EtOH
and various micellar media systems such as cetyltrimethylammonium bromide (cationic surfactant), sodium dodecylsulfate (an-
ionic surfactant) and Pluronic P123 (non-ionic surfactant). PdPtZn and PdZn thin films exhibited higher catalytic activity compared
to Pd thin film in the Suzuki–Miyaura coupling reaction due to the appropriate interaction between palladium, platinum and zinc
metals. Copyright © 2015 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: palladium/platinum/zinc nanoparticles; thin film; heterogeneous catalyst; carbon–carbon coupling; micelle
Micelles are especially simple spherical supramolecules, which are
formed by amphiphiles in water. The strong polarity gradient present
Introduction
Nanoparticles (NPs) are of considerable interest in catalysis, and this
subject has undergone tremendous growth during the past few
years.[1] It has been revealed that metal catalyst NPs with specific
size and shape exhibit a high surface area and a high concentration
of reactive sites resulting in improved catalytic performance over
conventional catalysts.[2,3]
between the hydrophilic surface and the hydrophobic core of a mi-
celle means that both non-polar and polar reagents can be solubilized.
This solubilization results in reactants becoming more concentrated
within the micelle than in the surrounding water phase and leads to
an acceleration of a reaction and causes selective effects.[12]
Generally, phosphine ligands are used in palladium-catalysed pro-
cesses, but most of them are toxic, expensive and sensitive to water
or air.[13] A ligandless approach for the C–C cross-coupling reaction
has attracted increased attention in recent years due to low cost. Re-
cently, employing readily available aryl chlorides in these transforma-
tions has received increasing attention, and a number of effective
catalytic systems have been developed for this purpose.[13,14]
Self-assembly at a liquid–liquid interface is a powerful experi-
mental route to novel nanomaterials and has received much
attention.[15–23] This method, developed by Rao and co-workers,
has been extensively used in synthesizing various nanostructure
thin films.[19–23] The method used to prepare a thin film at an
oil–water interface involves dissolving a suitable organic derivative
of the metal in the organic layer and injecting an appropriate reduc-
ing reagent in the aqueous layer. The product formed by the reac-
tion at the interface contains ultrathin nanocrystalline particles. By
controlling the reaction parameters, it has been possible to obtain
The formation of carbon–carbon bonds through metal-catalysed
cross-coupling processes stands out as one of the most frequently
utilized strategies in the design of nanomaterials of complex
molecules.[4] Although homogeneous catalytic systems generally
exhibit better activity and selectivity than heterogeneous systems,
heterogeneous catalysts have many advantages over their
homogeneous counterparts, including easy removal from reaction
mixtures and catalyst recyclability.[5] Palladium- and platinum-
based nanomaterials are very important due to their many
applications.[6–9] Palladium-catalysed Suzuki–Miyaura coupling re-
action, which involves the homogeneous cross-coupling reaction
of aryl halides with organoboron compounds, is one of the most ef-
ficient and clean strategies for the construction of aromatic C–C
bonds.[10] Oxidative addition and reductive elimination are key
steps in Suzuki–Miyaura coupling reactions. Also, metal–metal in-
teraction has a significant effect on oxidative addition as rate-
determining step. For example, the rate of the oxidative addition
step in Suzuki–Miyaura coupling reaction is accelerated due to
Pd–Pt interaction. As mentioned by Aurrecoechea and co-
workers,[11] the Pd–Zn interaction in the reductive elimination step
is found to be favoured. Furthermore, Zn as an environmentally
friendly metal, which decreases the cost of alloy systems, is impor-
tant in design and preparation of nanocatalysts.
*
Correspondence to: Hoseini, S. Jafar, Department of Chemistry, Faculty of
Sciences, Yasouj University, Yasouj 7591874831, Iran.
E-mail: jhosseini@yu.ac.ir
Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj
7591874831, Iran
Appl. Organometal. Chem. 2015, 29, 489–494
Copyright © 2015 John Wiley & Sons, Ltd.

S. J. Hoseini, A. Zarei and H. Rafatbakhsh Iran
isolated nanocrystals with narrow size distribution or well-formed
films of the nanocrystals. The oil–water interfacial assembly strategy
provides a powerful bottom-up approach for nanofilm production
due to low cost and low environmental impact.
of time, the colour became more vivid, finally resulting in a film
at the liquid–liquid interface. The actual Pd:Pt:Zn molar ratio for
PdPtZn NPs was estimated to be 31:35:34 using an inductively
coupled plasma analysis, which was close to the calculated
PdPtZn ratio (1:1:1) from the starting metal precursors. A similar
procedure was applied for the synthesis of PdZn NP thin films,
as shown in Scheme 1.
Recently, Fe3O4 NPs, Pd/aminoclay NPs and Fe3O4/Pd/r-GO NPs
have been investigated as efficient catalysts for C–C bond
formation.[24–26] Also, we have investigated thin-film formation of
Pd, Pd/r-GO NPs at an oil–water interface as an effective catalyst
for Suzuki–Miyaura reaction in water.[27] In the work reported in this
article, we succeeded in the synthesis of PdPtZn and PdZn NP thin
films in the absence of a stabilizer by the reduction of [PdCl2(cod)],
[PtCl2(cod)] (cod = cis,cis-1,5-cyclooctadiene) and [Zn(acac)2] (acac
= acetylacetonate) complexes at a toluene–water interface. This
strategy is an easy and inexpensive method for production of alloy
thin films and only a beaker and a syringe are required for a high-
quality thin film to be easily produced in a short time. Then, these
NPs were used as ligandless catalysts for the Suzuki–Miyaura reac-
tion in H2O–EtOH or micellar media.
General procedure for Suzuki–Miyaura cross-coupling
reaction
Phenylboronic acid (1.5 mmol) was added to a flask containing the
PdPtZn NPs catalyst and K2CO3 (2 mmol) in micelles (1 CMC, 5 ml).
This mixture placed in an oil bath at 80°C. Once the mixture reached
this temperature the reaction was initiated by the addition of aryl
halide (1.0 mmol). After completion of the reaction (monitored
using TLC), the reaction mixture was cooled to room temperature,
and then dichloromethane (3 × 5 ml) was added to the reaction
vessel. The organic phase was separated and dried over anhydrous
MgSO4. Subsequently, the solution was evaporated and the
resulting compound was washed with cool hexane to afford the de-
sired pure product.
Experimental
All of the chemical compounds were purchased from Merck. The
[PdCl2(cod)] and [PtCl2(cod)] complexes were synthesized using re-
ported procedures.[28] The [Zn(acac)2] complex was purchased from
Merck. Powder X-ray diffraction (XRD) patterns were obtained using
a Bruker AXS (D8 Advance) instrument employing the reflection
Bragg–Brentano geometry with Cu Kα radiation (λ = 1.54184 Å).
Energy-dispersive analysis of X-rays (EDAX) was carried out using
a Philips XL30 instrument with an accelerating voltage of 20 kV.
Transmission electron microscopy (TEM) images were obtained
with a Philips CM-10 microscope operated at 100 kV. Infrared spec-
Results and discussion
In this study, PdZn NP thin film was synthesized by the reduction of
[PdCl2(cod)] in the presence of [Zn(acac)2] complex as zinc precur-
sor at a toluene–water interface, as shown in Scheme 1. These com-
plexes were dissolved in toluene at room temperature and then
contacted with water. The aqueous solution of NaBH4 was injected
into the interface with minimal disturbance to initiate the reduc-
tion, and thin-film formation was indicated by an interface colour
change from yellow to black.
The crystal structure of the PdZn NP thin film was investigated
using XRD. Figure S1 shows the XRD pattern recorded for the PdZn
NP thin film. The five main diffraction peaks can be assigned as the
(111), (200), (220), (311) and (222) indices of face-centred cubic
Pd.[27] Other diffraction peaks confirm the Zn structure and corre-
spond to the planes (002), (100), (101), (102), (103), (110) and
(004).[29] Relative to the same reflections for Pd, the diffraction
peaks of the PdZn thin film are shifted to higher 2θ values, revealing
decreased lattice parameters and a high level of alloying.[30]
As determined using EDAX (Fig. S2), the PdZn thin film is com-
posed of Pd and Zn with a molar ratio of Pd:Zn = 52:48, which is
close to the calculated PdZn ratio (1:1) from the starting metal pre-
cursors. PdZn NP thin films have particles of uniform spherical
shape with smaller light dots which can obviously confirm PdZn al-
loy formation. Figures 1(a)–(c) show TEM images of PdZn with an
average diameter of 44 nm. Figure 1(d) shows a histogram of parti-
cle size distribution.
PdPtZn NP thin film was prepared at an oil–water interface as a
facile method. The XRD pattern resulting from PdPtZn NPs shows
a number of prominent Bragg reflections with indices [(111),
(200), (220), (311) and (222)] as Pt(0) and Pd(0) (Fig. 2).[27] The seven
diffraction peaks confirm the Zn structure and correspond to the
planes [(002), (100), (101), (102), (103), (110) and(004)].[29]
The chemical composition of the thin film was determined using
EDAX, confirming the presence of Pd, Pt and Zn elements (Fig. S3).
Figures 3(a)–(c) show TEM images of the as-prepared PdPtZn NP
thin film, which includes spherical structures. The average diameter
of the PdPtZn NP thin film particles is approximately 11.6 nm (Fig. 3(d)).
1
tra were recorded using a JASCO FT/IR-680 plus spectrometer. H
NMR spectra were obtained with a Bruker 400 MHz Ultra-shield
spectrometer using CDCl3 as the solvent and tetramethylsilane as
the internal standard.
Preparation of PdPtZn and PdZn NP thin films
Typically, to prepare PdPtZn thin films, 25 ml of deionized waterwas
added to a 25 ml toluene solution of [PdCl2(cod)]–[PtCl2(cod)]–[Zn(acac)
2] (1:1:1), in a 100 ml beaker. Once the two layers were stabilized, a
freshly prepared aqueous solution of NaBH4 (10 ml, 0.1 M) was
injected into the aqueous layer using a syringe with minimal dis-
turbance to the toluene layer. The onset of reduction was marked
by a coloration of the toluene–water interface. With the passage
dropwise addition
PdZn bimetallic thin film
formation at liquid-liquid
interface
of NaBH4
Pd and Zn complexes
dissolved in toluene
(b)
(c)
(a)
Water
Scheme 1. Schematic illustration of formation of PdZn bimetallic thin film.
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Appl. Organometal. Chem. 2015, 29, 489–494

PdPtZn thin-film-catalysed Suzuki cross-coupling reaction
Figure 2. XRD pattern of PdPtZn NP thin film deposited on glass.
Catalytic activity
The PdPtZn and PdZn NP thin films were used as efficient recover-
able catalysts in the Suzuki–Miyaura coupling reaction. We initiated
our study of the Suzuki–Miyaura cross-coupling reaction by opti-
mizing the conditions in terms of amount of NPs and solvent.
The choice of solvent has a significant impact on the efficiency of
the cross-coupling reaction. The reaction of bromobenzene with
phenylboronic acid was carried out in the presence of the PdZn NP
thin film using various solvents. According to the results given in
Table 1, the biphenyl product is detected in a low yield when the re-
action is carried out in water and EtOH (Table 1, entries 1 and 2). Bet-
ter conversion of biphenyl is observed for H2O–EtOH (1:1) (Table 1,
entry 3). K2CO3 was used as a base for optimizing the conditions of
the reaction. Also, in the presence of PdPtZn NPs as catalyst, the re-
action of bromobenzene with phenylboronic acid in H2O, H2O–EtOH
(1:1), H2O–sodium dodecylsulfate (SDS), H2O–Pluronic P123 (P123)
and H2O–cetyltrimethylammonium bromide (CTAB) for 60 min was
performed. According to the results given in Table 1, biphenyl prod-
uct is detected only in trace amounts when the reaction is carried out
in H2O, EtOH and H2O–EtOH (1:1) (Table 1, entries 1–3). When
employing H2O–SDS and H2O–P123, the reactions proceed smoothly
to give a marked enhancement in yield (Table 1, entries 4 and 5). Ev-
idently, when H2O–CTAB is used as solvent, an excellent yield (96%)
is obtained (Table 1, entry 6). The Suzuki coupling reaction of
bromobenzene with phenylboronic acid (H2O–EtOH (1:1) for PdZn
and H2O–CTAB for PdPtZn) at various temperatures (Table S1) was
investigated, and then 80°C was selected as reaction temperature
in aqueous solutions (see supporting information).
A series of reactions were performed with various amounts of
catalyst to test the reaction feasibility with catalyst concentration.
The optimal amount of the PdPtZn catalyst was determined from
the reaction of bromobenzene with phenylboronic acid at 80°C in
micellar system of CTAB. From Table 2 it is evident that an increase
in the amount of PdPtZn catalyst results in an increase in yield of
the cross-coupled product. The optimum amount of the PdPtZn
catalyst is 0.8 mol% of Pd (Table 2).
Further investigations were focused on application of the opti-
mized reaction conditions to Suzuki–Miyaura coupling reactions
of aryl halides. The results for related experiments are summarized
in Table 3. Various substrates including those with electron-
donating and electron-withdrawing groups can be coupled in good
reaction yields (70–98%) in short reaction times.
Figure 1. (a–c) TEM images of PdZn NP thin film with an average particle
diameter of 44 nm. (d) Histogram of particle size distribution.
Appl. Organometal. Chem. 2015, 29, 489–494
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S. J. Hoseini, A. Zarei and H. Rafatbakhsh Iran
Table 1. Suzuki–Miyaura coupling reaction of bromobenzene with
phenylboronic acid in various solvents in the presence of PdZn and
PdPtZn NP catalysts at 80°C in 60 min
Entry
Solvent
PdZn (mol%)a;
yield (%)b
PdPtZn (mol%)a;
yield (%)b
1
2
3
4
5
6
H2O
1.5; 40
1.5; 70
1.5; 94
1.5; 20
1.5; trace
1.5; 15
1.0; trace
1.0; trace
1.0; trace
1.0; 80
EtOH
H2O–EtOH (1:1)
H2O–SDS
H2O–P123
H2O–CTAB
1.0; 90
1.0; 96
aPd mol%.
bIsolated yield.
Table 2. Variation of amount of catalyst for Suzuki–Miyaura cross-cou-
pling reaction of bromobenzene with phenylboronic acid at 80°C in mi-
cellar system of CTAB for 60 min
Entry
PdPtZn (mol%)a
Yield (%)b
1
2
3
4
5
6
0.6
70
76
83
90
96
96
0.65
0.7
0.75
0.8
1.0
aPd mol%.
bIsolated yield.
Table 3. Suzuki–Miyaura reaction between aryl halides and
phenylboronic acid in the presence of PdPtZn and PdZn NP thin films
under optimized reaction conditionsa
Entry
Substrate
Product PdZn: time (h); PdPtZn: time (h);
yield (%)b
yield (%)b
1
PhI
1a
1a
1a
1b
1b
1c
1c
1d
1d
1e
1e
0.25; 97
1; 94
0.17; 98
0.75; 96
2; 80
2
PhBr
3
PhCl
8; 70
4
4-MeC6H4I
4-MeC6H4Br
4-NO2C6H4Br
4-NO2C6H4Cl
4-CNC6H4Br
4-CNC6H4Cl
C5H4NBr
0.5; 94
2; 80
0.33; 96
0.5; 94
0.5; 96
1.5; 82
0.33; 95
1.5; 90
1; 86
5
6
1.5; 85
3; 80
7
8
1; 85
9
3; 84
10
11
2; 83
C5H4NCl
8; 80
4; 85
aConditions: 80°C, H2O–EtOH (1:1) for PdZn and H2O–CTAB for PdPtZn.
bIsolated yield.
From an industrial point of view, the reusability of a catalyst is im-
portant for large-scale operation. Therefore, the reusability of the
catalysts was examined in the reaction of bromobenzene with
phenylboronic acid at 80°C under optimized reaction conditions.
Centrifugation was applied to separate the catalyst from the reac-
tion mixture and was then washed with water and diethyl ether.
Then, the PdPtZn and PdZn alloy catalysts were recovered by sim-
ple filtration from the reaction pot and can be reused successfully.
Figure 3. (a–c) TEM images of PdPtZn NP thin film. (d) Histogram of particle
size distribution.
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Appl. Organometal. Chem. 2015, 29, 489–494

PdPtZn thin-film-catalysed Suzuki cross-coupling reaction
Table 4. Isolated yields for recycling of PdZn and PdPtZn NP thin films
as catalyst at 80°C
Cycle
PdZn: yield (%)a
PdPtZn: yield (%)b
Fresh catalyst
First recycle
94
93
92
90
90
96
94
93
91
93
Second recycle
Third recycle
Fourth recycle
aH2O–EtOH (1:1).
bH2O–CTAB.
Figure 5. EDAX spectrum of PdZn NP thin film after four catalytic cycles.
Conclusions
In the present project, an oil–water interface self-assembly strategy
was used to produce PdPtZn NP thin film and PdZn binary NP thin
film at room temperature. The most important advantages of this
assembly strategy are the significant simplicity and universality
found in almost all of the related low-dimensional nanostructures.
These NPs were characterized using various techniques and were
further used as an excellent catalyst for Suzuki–Miyaura coupling
reactions. The size and the structure of NPs both affect the catalytic
performance. Despite the slightly larger size (44 nm) of the
PdZn alloy, it exhibits very high catalytic activity due to its spe-
cial structure. The higher catalytic activity of the PdPtZn thin
film in comparison to the PdZn thin film was attributed to
the small size (11 nm) and uniform dispersion of PdPtZn NPs
in micellar system of CTAB. The percentage of surface atoms
is higher in thin-film structures than in other structures and
renders these nanoalloys as very interesting in catalysis. Also,
since oxidative addition is almost the rate-determining step in
the catalytic cycle, the rate of formation of organopalladium
compound increased in the presence of platinum. Note that
the synergic electronic effect between Pt (as electron-rich
metal) and PdZn increases the electron density at the Pd cen-
tre. This effect facilitates the oxidative addition reaction in
C–C coupling reaction. After finishing the reaction, these cata-
lysts could be easily separated from the reaction mixture. Thus,
the use of PdZn and PdPtZn thin films reduces costs, simplifies
workup procedures and facilitates the separation of the final
product. In addition, high yields obtained with unactivated aryl
halides such as chlorobenzene derivatives is another advantage
of this study.
Figure 4. (a, b) TEM images of PdZn NP thin film after four catalytic cycles.
Acknowledgements
The authors thank the Yasouj University Research Council and the
Iranian Nanotechnology Initiative Council for their support.
The recyclability of the nanoalloy catalysts was investigated. The re-
sults in Table 4 show that the alloy catalysts retain a reasonable per-
formance when reused in four cycles.
Also, the particles of the PdZn NP thin film remain the same size,
and no considerable aggregation phenomenon is observed after
four cycles from TEM images (Fig. 4).
EDAX of the filtrate after the reaction demonstrates no leaching
of Pd and Zn (Fig. 5). This is very important when Pd catalysts are
used for pharmaceutical production.
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