Palladium nanoparticles supported on Layered Hydroxide Salts and their Use in Carbon-Carbon coupling organic reactions

Article abstract of DOI:10.1590/S0103-50532011001200012

Palladium nanoparticles supported on zinc hydroxide salts were prepared by intercalation of [PdCl₆]^2- and its further reduction with ethanol under reflux. All the materials were completely characterized by atomic absorption spectroscopy (AAS), X-ray diffraction (XRD), thermogravimetric/ derivative thermogravimetric (TG/DTG) analyses, scanning electron microscopy (SEM), UV-Visible spectrometry and transmission electron microscopy (TEM). TEM analysis confirmed that the palladium nanoparticles were properly supported. The material containing supported palladium nanoparticles was used to promote Heck and Suzuki coupling reactions starting from aryl halides, with isolated yields of 98, 75 and 62percent of biphenyl, cinnamic acid and 3-nitrobiphenyl, respectively.

Full text of DOI:10.1590/S0103-50532011001200012

J. Braz. Chem. Soc., Vol. 22, No. 12, 2322-2329, 2011.
Printed in Brazil - ©2011 Sociedade Brasileira de Química
0
103 - 5053 $6.00+0.00
Article
A
Palladium Nanoparticles Supported on Layered Hydroxide Salts and their Use in
Carbon-Carbon Coupling Organic Reactions
a
a
a
b
,c,d
Maby Martínez, Rogelio Ocampo, Luz Amalia Rios, Alfonso Ramírez and Oscar Giraldo*
a
Departamento de Química, Universidad de Caldas, Calle 65 No. 26-10, Manizales, Colombia
b
Grupo de Catálisis, Universidad del Cauca, Calle 5 No. 4-70, Popayán, Colombia
c
Laboratorio de Materiales Nanoestructurados y Funcionales, Carrera 27 No. 64-60,
Manizales, Colombia
d
Departamento de Física y Química, Universidad Nacional de Colombia sede de Manizales,
Carrera 27 No. 64-60, Manizales, Colombia
Nanopartículas de paládio suportadas em hidroxissal lamelar foram preparadas pela intercalação
2
−
de [PdCl6] seguida pela redução com etanol sob condições de refluxo. Os materiais foram
caracterizados por espectroscopia de absorção atômica (AAS), difração de raios X (XRD),
análises termogravimétrica e térmica diferencial (TG/DTG), microscopia eletrônica de varredura
(
SEM), espectrometria UV-Visível e microscopia eletrônica de transmissão (TEM). A análise
por TEM confirma a obtenção de nanopartículas suportadas. O material contendo nanopartículas
de Pd foi utilizado em reações de acoplamento de Heck e Suzuki a partir de haletos de arila
com rendimentos de 98, 75 e 62% para a obtenção de bifenilo, ácido cinámico e 3-nitrobifenilo,
respectivamente.
Palladium nanoparticles supported on zinc hydroxide salts were prepared by intercalation
2
−
of [PdCl6] and its further reduction with ethanol under reflux. All the materials were
completely characterized by atomic absorption spectroscopy (AAS), X-ray diffraction (XRD),
thermogravimetric/derivative thermogravimetric (TG/DTG) analyses, scanning electron microscopy
(
SEM), UV-Visible spectrometry and transmission electron microscopy (TEM). TEM analysis
confirmed that the palladium nanoparticles were properly supported. The material containing
supported palladium nanoparticles was used to promote Heck and Suzuki coupling reactions
starting from aryl halides, with isolated yields of 98, 75 and 62% of biphenyl, cinnamic acid and
3
-nitrobiphenyl, respectively.
Keywords: zinc hydroxide salts, palladium nanoparticles, Heck reactions, Suzuki reactions,
hexachloropalladate
7
Introduction
materials, systems for safe and controlled delivery of
8-10
substances and medical applications in general.
Layered materials are very important entities especially
because they offer an interesting possibility to host both
organic and inorganic species in their interlayer spacing,
including polymers and biomolecules. In this situation,
the layered materials confer them particular physical and
chemical properties which make the materials very
For these purposes, little attention has been paid to
layered hydroxide salts (LHS) with general formula
2+
m−
2+
M (OH) (A ) (with M being a metallic cation and
2-x
x/m
m−
11,12
A
the interlaminar anion).
For the case of layered
zinc hydroxide acetate, it has been determined that this
compound has the hydrozincite-type structure, in which
cations are located in both octahedral and tetrahedral
1
attractive for applications such as catalysts, supporting
2
3
3
13
materials, adsorbents, and anion exchange agents,
sites and the acetate ions are intercalated as free anions.
4
5
6
UV absorption materials, electrodes, sensors, optical
On the other hand, palladium is a versatile agent in the
14-19
catalysis for a number of organic reactions,
and this
*
e-mail: ohgiraldoo@unal.edu.co
feature has called attention to explore its applications under

Vol. 22, No. 12, 2011
Martínez et al.
2323
20-23
-1
nanometricdimensionsbothsupportedandnon-supported.
equivalent of 1.2 mg mL . Precaution was taken to run the
It is well known that nanometric arrays confer a high
catalytic efficiency to the materials because of their high
surface:volume ratios. Several reports have demonstrated
the potential of nanometric palladium particles in carbon-
reaction under inert N atmosphere in order to prevent the
generation of carbonates that might derive from reaction of
2
the materials with atmospheric CO .After 24 h of reaction,
2
the resulting material was centrifuged three times and
washed with distilled, deionized water (DDW) and dried
at room temperature. The material was labeled as LHS60.
15,22-24
carbon coupling reactions,
procedures for the synthetic organic chemistry, with their
products becoming key intermediates for the preparation of
which are important useful
25,26
2
7-29
30
other organic materials,
natural products and bioactive
Preparation of LHS supported palladium nanoparticles
31,32
compounds, such as taxol (antitumor agent) or cinnamic
acid derivatives. These products exhibit antibacterial or
antifungal activities and some other are useful as ingredients
LHSsupportedPdnanoparticleswerepreparedaccording
33
37
to the reduction method reported by Rajamathi et al. as
follows: 0.2 g of the intercalated material LHS60 were
suspended in 5 mL of ethanol and refluxed for 3 h with
continuous stirring. The resulting material was finally
centrifuged and washed three times with ethanol. The
black solid was dried at room temperature and labeled as
3
4,35
for fragrances.
The biphenyl systems are particular
kinds of products that derive from coupling reactions and
are acknowledged as precursors for the preparations of
36
analgesics and other pharmaceuticals.
0
This article reports the synthesis and characterizations
of palladium nanoparticles supported on layered materials
LHS-Pd .
(
zinc hydroxide acetate) by anionic exchange with K PdCl6
Preliminary carbon-carbon coupling reactions using
LHS-Pd
2
0
and its further reduction through the hosted complex with
ethanol under reflux. The resulting solid was explored
in preliminary tests to promote carbon-carbon coupling
reactions starting from aryl halides, giving rise to biphenyl,
cinnamic acid and 3-nitrobiphenyl with yields up to 98,
All the Suzuki and Heck reactions were run with
0
o
10 mg of LHS-Pd at 100 C with the indicated organic
starting materials under reflux and monitoring by thin
layer chromatograph (TLC) (with hexane:ethyl acetate
binary systems as eluent). After worked-up, the respective
melting points of the organic products were determined in
a Buchi-510 instrument and reported without correction.
7
5 and 62%, respectively.
Experimental
1
13
All chemicals (Sigma-Aldrich, 98 and 99% purify)
were used without further purification. The synthesis of
supported palladium nanoparticles was performed in three
steps: (i) preparation of the zinc precursor and hydroxide
H and C NMR spectra (in CDCl ) were run in a Bruker
3
ARX-250 instrument and the signals were directly
compared with the literature data, proving the identity of
the expected products.
acetate (LHS), (ii) anionic exchange of LHS with K PdCl6
2
to produce (LHS60) and (iii) generation of Pd nanoparticles
Suzuki reactions
0
2−
(
LHS-Pd ) by reduction of the hosted [PdCl ] complex
Biphenyl was prepared by reaction of iodobenzene
(3.0 mmol) with boronic acid (4.2 mmol) in the presence
of KOH (9 mmol) in 15 mL of a binary 5:1 mixture (v/v)
dioxane:water. The coupled product was purified by
flash column chromatography (silica gel 60 Merck as the
stationary phase).An analog reaction was also performed in
order to prepare 3-nitrobiphenyl by using m-nitroboronic acid
instead of boronic acid, under identical reaction conditions.
6
with ethanol under reflux.
Synthesis
Synthesis of supporting LHS
Zinc hydroxide acetate precursor (LHS) was prepared
according to the literature by mixing together ZnO
(
5.04 mmol) and Zn(OAc) .2H O (6.91 mmol) in 10 mL
2 2
2
0
of water at room temperature, while stirring for 24 h.
Heck reactions
The material was centrifuged three times and washed
with distilled, deionized water (DDW) and dried at room
temperature. The material was labeled LHS.
Cinnamic acid was prepared starting from iodobenzene
(8.04 mmol) and acrylic acid (6.13 mmol) in the presence
of triethyl amine (12.5 mmol) in acetonitrile (2 mL). The
reactant mixture was cooled down to room temperature
and transferred into a beaker containing 50 mL of
−
2
Intercalation of [PdCl ] anion
6
-1
0
.5 g of LHS was mixed and stirred with 50 mL of
3.0 mol L HCl. The resulting solid was filtered and washed
with distilled, deionized water (DDW).
an aqueous solution of K PdCl containing a palladium
2
6

2
324
Palladium Nanoparticles Supported on Layered Hydroxide Salts
J. Braz. Chem. Soc.
3
8
Physicochemical characterization of the inorganic
materials
of chloride was determined by Morh´s method. In fact,
zinc hydroxide chloride phase as well was found in the
XRD patterns (being described later). In comparison to
zinc hydroxide acetate, the zinc hydroxide chloride has
a different structure, and since the chloride anions in this
case are not exchangeable, the layers bear no net charge.
Also, a content of palladium of 11.5% in LHS60 and
0
All materials (LHS, LHS60 and LHS-Pd ) were
characterized by atomic absorption spectroscopy (AAS),
X-ray diffraction (XRD), thermogravimetric/derivative
thermogravimetric (TG/DTG) analyses, scanning electron
microscopy (SEM), UV-Visible spectrometry and
transmission electron microscopy (TEM).
0
13.3% in LHS-Pd was determined by UV-Vis spectrometry.
The difference of 1.8% of palladium content between these
samples is in agreement with an expected increment of the
For XRD analysis, a Rigaku Miniflex II instrument
0
(
30kVand15mA)wasusedwithCuK radiationsourcewith
relative abundance of palladium in the LHSPd material
α
o
-1
a scan rate of 2 min in normal environmental conditions.
The crystal size of Pd in the LHS-Pd was estimated from
its diffraction pattern by the Debye-Scherrer’s method.
after the hexachloropalladate complex has released the
chlorine atoms out from the layered material LHS60 during
the course of the reduction. This suggests that no palladium
leaching occurred along the reduction step.
The overall zinc content in the materials was determined
by atomic absorption spectrometry, with the resulting of
49% of zinc for LHS, 46% for LHS60 and 47% for LHS-Pd .
As expected, a higher content of zinc (49%) was found for
the LHS precursor. Slightly lower data (46 and 47%) were
0
38
SEM was recorded in a JEOL5910 LV instrument with
secondary electron detector, while transmission electronic
microscopy was run in a JEOL 1200 EX instrument.
TG/DTG analyses were recorded in a TA Instruments
0
o
-1
Q500 instrument with a heating rate of 10 C min under
N atmosphere.
2
0
AAS was performed on a Perkin Elmer 3110, whereas
UV-Vis analysis was recorded in a Lambda 20 instrument.
The amount of metal palladium that was being retained
inside the layered material was measured by UV-Vis after
the construction of a preliminary calibration curve from the
absorbance of standard solutions of K PdCl in aqua regia.
found in LHS60 and LHS-Pd , respectively. This is due to
the insertion and modification of the palladium species in
the exchange and reduction reactions.
The XRD diffraction pattern for the precursor is showed
in Figure 1d. Figures 1b and 1c correspond to the diffraction
pattern of the reactants and reveal the generation of a pure
phase of the layered hydroxide salt. Figure 1d clearly
exhibits two peaks that correspond to the basal spacing
20.6 and 13.8 Å, indicating the presence of two phases.
It is common to find procedures in the literature that are
similar to the one which the present article reports for the
2
6
0
For this purpose, weighted samples of LHS-Pd were also
dissolved in properly measured volumes of aqua regia and
the absorbance data were recorded for the resulting
solutions, so the amount of palladium was determined by
direct comparison with the calibration curve.
1
,39,40
synthesis of this type of materials,
giving rise to a
Results and Discussion
Zinc hydroxide acetate LHS was initially prepared under
mild reaction conditions (as described in experimental
section). In this precursor, the acetate groups being
localized in the interlayer space were exchanged with
2−
[
PdCl ] , and the resulting material LHS60 was reduced
6
in ethanol under reflux, giving rise to a dark-colored solid
0
LHS-Pd .
This later material proved to contain supported
palladium nanoparticles. From the reflection plane (111)
of palladium, it was estimated a diameter of 7.4 nm for
the palladium nanoparticles by the Debey-Scherrer´s
3
8
equation.
0
LHS-Pd material exhibited evidences of the presence
of chloride anions that were released during the reduction
procedure. The present authors suggest that chloride anions
contribute to balancing the charge of the material forming
a fraction of zinc hydroxide chloride. A content of 2.33%
Figure 1. XRD patterns of (a) K PdCl , (b) ZnO, (c) Zn(OAc) , (d) zinc
2
6
2
0
hydroxide acetate (LHS), (e) LHS60, (f) LHS-Pd and (g) characteristic
0
0
peaks for Pd in LHS-Pd .

Vol. 22, No. 12, 2011
Martínez et al.
2325
layered hydroxide salt phase with a unique basal spacing
ranging in the interval of 13.2-13.4Å. In our case, however,
the observed basal spacing is 13.8 Å.
layered hydroxide salt assigned to zinc hydroxide chloride
4
2
of formula Zn (OH) Cl .H O, d = 8.2 Å (Figure 1f). This
5
8
2
2
reaction involves the formation of ZnO as well and this
inorganic product certainly results from the decomposition
of part of the laminar structure, as evidenced upon
comparison of Figures 1b and 1f. Crystallographic planes
of metal palladium in a cubic system and spatial group
The second reflection peak of 20.6 Å is similar to the
4
1
one reported by Song et al. who prepared a bilayered
zinc acetate salts (a BLBZA nanobelt-type material,
(
d001(I) = 13.3 Å and d001(II) = 20.3 Å) starting from
o
43
Zn(OAc) and ammonia at 30-60 C by hydrothermal
Fm3m are presented in Figure 1g. Finally the distance
2
treatment for 12 h. In the present study, it was obtained
a similar material but our procedure involves milder
conditions as room temperature and atmospheric pressure.
It is suggested that the small difference in the reported
basal spacing might result from slightly different extents
of hydration of the layered hydroxide salt.
at d = 6.9 Å (Figure 1) may be assigned to the second
reflection of the 13.8Å phase and also to the third reflection
corresponding to the 20.6 Å phase. The TG/DTG plots for
the reduced material and its precursors are observed in
Figure 3, evidencing a total weight loss of 36, 25 and 21%,
0
respectively for LHS, LHS60 and LHS-Pd (Figure 3d-f).
For the exchanged and the reduced materials
LHS60 and LHS-Pd , respectively), XRD patterns are
All materials exhibit several decomposition steps which
are also observed in other anionic clays.
0
44
(
shown in Figure 1d-f. From these figures, it is evident that
the materials give raise to different patterns each other.
This proves that it took place some transformation. It is
2
−
clearly observed that upon intercalation of [PdCl6] in
the interlayer space of the LHS material only the phase
of 20.6 Å is kept. This result suggests a good interaction
2
−
between support and the hosted anion [PdCl6] and its
homogeneous distribution in the material. Although the
final reduced material that was obtained thereafter does
not exhibit the original spacing characteristic of the LHS
precursor. This is induced by the formation of palladium
nanoparticles of different sizes ranging from 6 to 13 nm,
as deduced from TEM image (Figure 2). This size turns
out to be in a close agreement with the crystal size of
7
.4 nm for the nanoparticles that was estimated from the
0
Figure 3. DTG curves of (a) LHS-Pd , (b) zinc hydroxide acetate
(
(f) zinc hydroxide acetate (LHS).
38
Debey-Scherrer equation, by using the (111) reflection
plane of the Pd XRD pattern (Figure 1g).
0
LHS) and (c) LHS60 and TG curves of (d) LHS-Pd , (e) LHS60 and
The first weight loss may be explained by the release
of physisorbed and interlayer waters, which starts at room
temperature and is completed at 110, 140 and 180 ºC in
0
LHS, LHS60 and LHS-Pd , respectively, in agreement
with 9, 5 and 6% of weight loss in each case. A second
thermal event that is completed at 400 ºC has been mainly
assigned to dehydroxylation of the laminar structure and
the decomposition of acetate groups which are occupying
the interlayer space. It is noteworthy that the starting
temperature for dehydroxylation (110, 140 and 180 ºC for
0
LHS, LHS60 and LHS-Pd , respectively) is consecutively
0
higher in going from the exchanged material to the reduced
one. With this observation in mind, it is possible to conclude
that the intercalation and reduction reactions enhance
the thermal stability of the material. Beyond 400 ºC, no
important changes are observed in the LHS precursor,
although the exchanged and reduced materials exhibit a
Figure 2. TEM images of (a) LHS-Pd and (b) zoom of the marked area
in (a).
On the other hand, by using the diffraction pattern of the
reduced material and matching with crystallographic data
from the literature, it was confirmed the formation of a new

2
326
Palladium Nanoparticles Supported on Layered Hydroxide Salts
J. Braz. Chem. Soc.
third thermal event that is completed at about 500 ºC. This
later thermal event may be attributed to a loss of chloride
anion from the hexachloropalladate complex of LHS60 (in
the case of the exchanged material). Likewise, the analog
0
thermal event for the reduced LHS-Pd material is due to
a release of chloride anion that was produced in the course
of the reduction step for a balance of charge in the layers of
material. The presence of chloride in these materials was
38
quantitatively confirmed by Morh’s method.
The SEM images of LHS precursor (the exchanged
0
LHS60 and the reduced LHS-Pd materials) are presented
in Figure 4.
As clearly observed in Figure 4a, zinc hydroxide acetate
exhibits a flake like, slightly rough morphology, which
4
4
is the typical surface appearance of layered materials.
This morphology is not observed anymore after [PdCl6]
2−
intercalation took place, as it is in fact observed for the
LHS60 material in Figure 4b, whose morphology becomes
more compact with small clusters on the surface.Additional
morphological changes with larger clusters are observed
as well in the reduced material, as evidenced in Figure 4c.
Transmission electronic microscopy TEM was used
as a tool to detect de presence of palladium nanoparticles
0
in the reduced material labeled as LHS-Pd . TEM images
(
Figure 2) confirmed that palladium was in fact reduced by
2
−
0
refluxing ethanol from the Pd(IV) state of [PdCl ] to Pd ,
6
giving rise to particles with sizes ranging from 6-13 nm, as
evidenced in the magnified TEM image (Figure 2b). Larger
particles are also observed in Figure 2, probably resulting
from primary particle agglomerations.
0
The reduced LHS-Pd material was then used in
preliminary tests to promote carbon-carbon coupling
reactions and the results are presented in Table 1. Several
previous works have explored the synthesis of biphenyl
Figure 4. SEM images of (a) zinc hydroxide acetate (LHS), (b) LHS60 and
(c) LHS-Pd .
0
Table 1. Results of Heck and Suzuki reactions
Coupling reaction
Heck
Reagent
Product
Name of the product
cinnamic acid
Reaction time / h
1.5
Isolated yields / %
75
I
CO2H
+
CO2H
I
B(OH)2
Suzuki
Suzuki
biphenyl
1
1
97
62
+
I
B(OH)2
NO2
3-nitrobiphenyl
+
NO2
0
Heck reactions: iodobenzene (8.04 mmol), acrylic acid (6.13 mmol), triethyl amine (12.5 mmol), LHS-Pd (10 mg) and 2 mL of acetonitrile, at 90-100 ºC
0
under reflux; Suzuki reaction: iodobenzene (3.0 mmol), boronic acid (4.2 mmol), KOH (9 mmol), LHS-Pd (10 mg) and 15 mL of a 5:1 v/v binary mixture
1
,4-dioxane:water, at 100 ºC under reflux.

Vol. 22, No. 12, 2011
Martínez et al.
2327
systems with good to high yields promoted by palladium
nanoparticles supported on polyacrylamide with 96%
starting from acetic acid and benzaldehyde. In fact, it was
prepared in this article cinnamic acid with 75% yield and
1.5 h of reaction time, in a clear contrast with the already
mentioned homogeneous phase condition that demands
reaction times ranging between 8 and 16 h and giving rise
to yields of 64 to 70%. The percent of yield for each run
was estimated as equation 1:
1
9
yields. Similar results (95% yields) have been reported
4
5
when using diatomaceous supports, organostannoxane
4
6
(
with reported yields of up 99%) and layered double
20
hydroxides LDH (with yields ranging between 90-93%).
Referenced reaction times when using palladium
nanoparticles in the cited supporting materials were 40,
(
1)
2
5, 240 and 600 min, respectively. Other authors have
reported analog reactions promoted by non-supported
metallic palladium, reaching yields of 93% if extending
to 5 h the reaction time.
Our results of the described coupling reactions, which
were carried out with the reduced LHS-Pd material
47
0
In a similar way, dispersed palladium nanoparticles on
polymer matrixes have promoted carbon-carbon coupling
reactions that take ca. 6 h with yields of 55%.
under heterogeneous phase, comprise some evidence of
the advantages of this methodology in comparison to the
analog syntheses under homogeneous phase that have been
22
48
Solvent effects on coupling reactions catalyzed by
palladium in nanometric arrays have also been studied. For
example, water has been extensively used in combination
reported by Simonyan.
0
A schematic representation of our LHS-Pd material is
presented in Figure 5, which is a reasonable picture that
accounts for the characterization results and explains how
the carbon-carbon coupling reactions are easily promoted
by this nanometric array of metal palladium (see Table 1).
45
46
20
22
with bases such as TBAB, K CO , KF and Na SO ,
2
3
2
4
but these systems demand reaction times of up 6 h for
22
assemblage of biphenyl systems.
As a catalyst for different C-C coupling reactions of
the type Heck and Suzuki, particularly for the syntheses
of biphenyl, 3-nitrobiphenyl and cinnamic acid, supported
palladium nanoparticles using solid zinc hydroxide acetate
0
(
LHS-Pd ) proved to have a series of advantages over other
palladium-based systems. Excellent results are obtained
0
when using LHS-Pd in terms of a significant favorable
balance between yields, mild reaction conditions and
proportions of active phase (1.1 mmol of Pd). Biphenyl
is obtained with 98% yield in a mixture water:dioxane
(5:1 v/v) as a solvent and KOH as the base in 1 h (Table 1).
Other authors report similar reaction yields, but using higher
22,46
temperatures and longer reaction times. Under the same
reaction conditions, 62% yield is reached for the synthesis
of 3-nitrobiphenyl. The difference between the percentages
of conversion to biphenyl and 3-nitrobiphenyl is not itself
associated to the catalytic system but it is attributed to the
intrinsic electronic nature of the starting boronic acids. It is
well known that the boronic acids undergo an electrophilic
substitution in the transmetallation step of the catalytic
cycle in such a way that the palladium catalyst displaces
the boronic moiety, with the aromatic-ring behaving as
the nucleophile and the palladium species behaving as the
electrophile. The strong electron-withdrawing effect of the
nitro group deactivates the ring for this step giving rise to
overall acceptable reaction results.
0
Figure 5. Schematic representation of the material LHS-Pd .
Conclusions
It is reported the successful preparation and
characterization of palladium nanoparticles supported in
zinc hydroxide acetate. This was carried out by intercalation
2
−
0
of [PdCl ] and its further reduction to Pd . The size of the
6
particles ranged between 6 and 13 nm as it was shown by
transmission electronic microscopy. The coexistence of
two different interlayer spaces was observed, being this
phenomenon explained in terms of the presence of phases
with a different extent of hydration. Additionally, the
generation of zinc hydroxide chloride during the reduction
process was also observed.
0
On the other hand, the same LHS-Pd catalytic system
for the reaction of acrylic acid and iodobenzene allowed
us to obtain cinnamic acid with higher yields than the ones
typically reached under the homogeneous phase conditions

2
328
Palladium Nanoparticles Supported on Layered Hydroxide Salts
J. Braz. Chem. Soc.
Being constituted by supported Pd nanoparticles, this
13. Poul, L.; Jouini, N.; Fiévet, F.; Chem. Mater. 2000, 12, 3123;
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new material was used in preliminary tests to promote the
synthesis of cinnamic acid, 3-nitrobiphenyl and biphenyl,
with yields of 75, 62 and 97%, respectively. It is proved that
in this way the new material holds an important potential
for carbon-carbon coupling organic reactions.
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Acknowledgements
1
7. Tronto, J.; Leroux, F.; Dubois, M.; Taviot, C.; Valim, J. B.;
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We greatly acknowledge and thank to Universidad
de Caldas and Universidad Nacional de Colombia
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(
Manizales) and their respective research management
offices (Vicerrectoría de Investigaciones y Postgrados and
Dirección de Investigaciones sede Manizales DIMA) for
the financial support of this research. We also acknowledge
and thank to the chemistry laboratory at Universidad
Nacional de Colombia (Manizales) and its laboratories
of advanced microscopy, and advanced magnetism and
materials for the atomic absorption analyses, UV-Vis
spectra, SEM and TG/DTG analyses. Finally, thanks to
Universidad del Cauca (Colombia) for the TEM analyses.
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