Green conditions for the Suzuki reaction using microwave irradiation and a new HNT-supported ionic liquid-like phase (HNT-SILLP) catalyst

Article abstract of DOI:10.1002/aoc.3114

A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradiation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water-ethanol at 120 °C in presence of K₂CO₃ as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of microwave irradiation decreased the reaction time and also improved conversion with respect to traditional heating. Copyright

Full text of DOI:10.1002/aoc.3114

Full Paper
Received: 17 September 2013
Revised: 12 November 2013
Accepted: 13 November 2013
Published online in Wiley Online Library: 10 February 2014
(wileyonlinelibrary.com) DOI 10.1002/aoc.3114
Green conditions for the Suzuki reaction using
microwave irradiation and a new HNT-
supported ionic liquid-like phase (HNT-SILLP)
catalyst
Marina Massaroa, Serena Rielaa*, Giuseppe Lazzarab,
Michelangelo Gruttadauriaa, Stefana Miliotob and Renato Notoa
A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradi-
ation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions
were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new
catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the
synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of mi-
crowave irradiation decreased the reaction time and also improved conversion with respect to traditional heating. Copyright
© 2014 John Wiley & Sons, Ltd.
Keywords: Halloysite; Suzuki reaction; microwave; SILLP (supported ionic liquid-like phase)
Among various inorganic supports for immobilizing palladium
catalysts, silica is very promising because of its high surface area,
Introduction
In the history of organic chemistry, the formation of new bonds
between two carbon atoms has always been one of the funda-
mental reactions,[1] and therefore much research around the
world has tried to broaden new methodologies that are able to
improve the reaction conditions.
The palladium-catalyzed Suzuki–Miyaura cross-coupling reac-
tion of aryl halides with arylboronic acids[2] is one of the most
valuable synthetic routes for the preparation of symmetric and
asymmetric biaryls, which are important skeletons in the struc-
tures of biologically active compounds,[3] agrochemicals, phar-
maceuticals,[4] polymers,[5] ligands[6] and functional materials.[7]
The key advantages of the Suzuki–Miyaura cross-coupling are:
(i) the mild conditions under which it is conducted; (ii) the high
tolerance toward functional groups, (iii) the commercial availabil-
ity and stability of boronic acids to heat, oxygen and water; and
(iv) the ease of handling and separation of boron-containing
by-products from the reaction mixtures.[8]
Usually, the Suzuki reaction is performed under homogeneous
conditions in the presence of trivalent phosphine ligands[9] or
in the presence of N-heterocyclic carbenes (NHCs)[10] or with
palladacyclic complexes.[11] To avoid problems related to sepa-
ration of homogeneous catalysts, palladium complexes or nano-
particles were immobilized on various supports such as silica,
alumina, zeolites, organic polymers, magnetic nanoparticles
and dendrimers.[12]
good thermal stability, ready availability and economic viability,
and relatively easy covalent modification with organic or organo-
metallic moieties.
In this area, emerging materials with an appealing perspective
for application in catalysis are halloysite nanotubes (HNTs).
Halloysite is a double-layered aluminosilicate mineral that has a
predominantly hollow tubular structure.
The functionalization of HNTs is a good strategy for introduc-
ing an organic moiety on to the external surface and therefore
to obtain innovative catalyst supports as demonstrated for
metalloporphyrin[14] immobilization and heterogeneous atom
transfer polymerization of methyl methacrylate (MMA) into poly
(methyl methacrylate) (PMMA) using CuBr as catalyst.[15] HNTs
have also been used as a catalyst support for platinum in the syn-
thesis of allyl-ended hyperbranched organic silicone resins.[16]
Similar to recoverable catalysts, microwave-promoted synthe-
sis is also an area of increasing interest in both academic and
industrial laboratories since microwaves are an efficient and
non-polluting mode of heating the reaction mixture.[17] The
combination of microwave technology and heterogeneous
*
Correspondence to: Serena Riela, Dipartimento STEBICEF, sez. Chimica,
Università degli Studi di Palermo, Viale delle Scienze-Parco d’Orleans II, Ed.
17, 90128 Palermo, Italy. Email: serena.riela@unipa.it
In addition, Suzuki reactions were also carried out in supported
ionic liquid-like phase (SILLP) – structured materials able to
present most characteristics and properties of ionic liquids as
molecular solvent, playing an active role in the immobilization
and stabilization of Pd species.[13]
a Dipartimento STEBICEF, sez. Chimica, Università degli Studi di Palermo, 90128,
Palermo, Italy
b Dipartimento di Fisica e Chimica, Università degli Studi di Palermo,
90128, Palermo, Italy
Appl. Organometal. Chem. 2014, 28, 234–238
Copyright © 2014 John Wiley & Sons, Ltd.

Green conditions for the Suzuki reaction under microwave irradiation
catalysis is therefore likely to have a great impact on sustainable
chemistry, and prove to be a better catalytic system from both
economic and environmental viewpoints.
parameters such as the reaction time, solvent, base and amount
of catalyst.
First, it is interesting to note that the catalyst HNT-IL/Pd previ-
ously obtained[20] is a material with lower Pd loading (0.7 wt% )
compared to the silica-modified support (10 wt%);[22] this is a
consequence of the different degree of IL loading on HNT as
compared to silica, which has a greater surface area.
Table 1 shows the effect of different solvents on the Suzuki cou-
pling between phenylboronic acid and 4-bromoacetophenone
that was selected as model. We have used polar and non-polar
solvents with different abilities to convert electromagnetic energy
into heat, with an irradiation time of 2, 6 and 10 min, respectively,
at a temperature of 120 °C. This value was chosen according to
literature conditions.[23]
The Suzuki reaction has been successfully carried out using
water as reaction medium in conjunction with microwave
heating;[18] furthermore, the addition of an ionic liquid to the
reaction mixture as co-solvent has led to very high conversions
and clean reactions.[19]
Recently,[20] we modified the external surface of halloysite
nanotube with octylimidazolium moieties (HNT-IL) by microwave
irradiation under solvent-free conditions. In the best synthesis
the degree of loading of HNT, as estimated by TGA, was
0.15 mmol gÀ1
.
The preparation of supported palladium
nanoparticles (HNT-IL/Pd), where the metal catalyst can be linked
by electrostatic interactions in the HNT-IL support, was achieved
by anion exchange from Br- to PdCl24À (aqueous solution of
Na2PdCl4). The solid material, HNT-IL/(PdCl24À), was recovered by
filtration and, finally, the Pd(II) was reduced to Pd0 with NaBH4
in ethanol. Following this procedure, an HNT-IL/Pd catalyst with
0.7 wt% Pd was obtained, as determined by energy-dispersive
X-ray measurement (Fig. 1). Preliminary studies have confirmed
the good catalytic activity of HNT-IL/Pd support employed in
the Suzuki reaction using H2O/EtOH (1:1) as solvent, at 50 °C
in the presence of K2CO3 for 19 h.
It is known that ceramic materials based on aluminosilicates
react quickly under microwave irradiation with consequent
rapidity and uniformity of heating;[21] therefore, in this work, we
have investigated our catalytic system for the Suzuki reaction
between phenylboronic acid and several aryl halides under
microwave irradiation.
As reported in the literature,[18] water as solvent is central to
the success of the reaction (entries 7 and 14); in our case the
best conditions were obtained when we used as solvent the
mixture H2O–EtOH (1:1) (entries 6 and 13), probably because
it better dissolves both organic reagents and inorganic base.
The best result was obtained using a reaction time of 10 min
(entry 15); longer times of irradiation led to the degradation
of compounds.
For further investigations we decided to use an ethanol–water
mixture and an irradiation time of 10 min (entry 15). In order to
investigate the role of the base, two bases were used, namely
K2CO3 and Cs2CO3. The results show that K2CO3 was the optimum
base under microwave irradiation at 120 °C in the presence of
1 mol% catalyst (Table 2, entries 1 and 3). As both metal
Table 1. Optimization of solvent and time for Suzuki cross-coupling
reaction under microwave irradiationa
Results and Discussion
The Suzuki cross-coupling reaction between several aryl halides
and phenylboronic acid in the presence of HNT-IL/Pd catalyst
was investigated under microwave irradiation. Our studies were
focused on determining the influence of different reaction
OMe
O
Entry
Solvent
Time (min)
Conversion (%)b
N
Si
SH
N
+
1
THF
2
2
Trace
12
24
—
—
37
30
9
O
Br
2
MeOH
3
EtOH
2
4
Acetonitrile
DMF
2
AIBN
S
5
2
6
H2O/EtOH (1:1)
H2O
2
OMe
Si
7
2
O
O
N
N
8
THF
6
Br
9
MeOH
6
10
48
5
10
11
12
13
14
15
EtOH
6
Acetonitrile
DMF
6
1) PdCl2, NaCl, H2O
2) NaBH4, EtOH
6
—
55
42
>99
H2O/EtOH (1:1)
H2O
6
6
OMe
Si
H2O/EtOH (1:1)
10
O
O
N
X-
N
S
aReaction conditions: aryl halide (1.01 mmol), phenylboronic acid
(1 mmol), K2CO3 (1.12 mmol), solvent (1.2 ml), HNT-IL/Pd (1 mol
%). MW, microwave.
bDetermined by H NMR.
Pd
1
Figure 1. Synthesis of HNT-Pd catalyst.
Appl. Organometal. Chem. 2014, 28, 234–238
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

M. Massaro et al.
Table 2. Optimization of base for Suzuki cross-coupling reaction
aryl bromides, iodides and less reactive aryl chlorides, using
phenylboronic acid under microwave irradiation at 120 °C in the
presence of K2CO3; HNT-IL/Pd catalyst was used at 1 mol% and
all reactions were run for 10 min.
under microwave irradiationa
Conversions were high, ranging from 78% to 100%; in all case
no byproducts were detected and the conversions reported in
Table 3 correspond to yields. Full conversions were achieved
when aryl bromides and iodides were employed (entries 1, 3–5,
7, 8, 10, 11, 13 and 14–16 respectively), while less reactive aryl
chlorides (entries 17 and 18) gave lower yields. However, it is
noteworthy that in the latter cases no product was detected by
traditional heating.
The Suzuki reaction was performed by aryl halides bearing
both electron-donating and electron-withdrawing substituents
and the results were comparable. Therefore, under the defined
conditions, reactions did not show any sensitivity to electronic
effects; for example, 4-bromoanisole or 4-bromotoluene (or
4-iodotoluene) have a comparable result to 4-bromobenzaldehyde
(Table 3, entries 5, 7, 15, 3).
Entry
Ar-X
Base
Conversion (%)b
1
2
3
4
4-Bromoacetophenone
4-Bromoacetophenone
4-Bromobenzaldehyde
4-Bromobenzaldehyde
K2CO3
Cs2CO3
K2CO3
Cs2CO3
>99
71
>99
87
aReaction conditions: aryl halide (1.01 mmol), phenylboronic acid
(1 mmol), base (1.12 mmol), solvent (1.2 ml), HNT-IL/Pd (1 mol%).
bDetermined by 1H-NMR.
The data in Table 3 show that application of microwave
irradiation can decrease the completion time of reaction and also
improve conversions which respect traditional heating, as
previously reported by our group (50 °C, 19 h).[20]
carbonates screened have similar basicity, the results suggest
that there may be a cationic effect in the reaction.
The introduction of a small amount of ionic liquid onto the
HNT external surface was probably enough to obtain a dramatic
change in the heating profiles by changing the overall dielectric
properties of the reaction mixture, which consequently led to
improved yields.
In Table 3 are shown the data obtained using the catalytic
system for Suzuki cross-coupling reaction of different types of
Table 3. Suzuki cross-coupling reaction of phenylboronic acid with
various halides under optimized reaction conditions under micro-
wave irradiationa
Catalyst Recycling
Recycling investigations were carried out using catalyst HNT-IL/Pd
at 1 mol% in the reaction between phenylboronic acid and
3-bromoanisole (Table 4). The heterogeneous support allows
efficient recycling by filtration. Indeed, the catalyst was reused
for several cycles, and after each run the reaction mixture was
centrifuged and the liquid mixture was decanted. The residual
solid catalyst was employed again with fresh solvent, sub-
strates and base. The HNT-IL/Pd catalyst could be reused for
Entry
1
Ar-X
Conversion (%)b
>99
80
4-Bromoacetophenone
3-Bromoacetophenone
2
3
Table 4. Recycling investigationsa
4-Bromobenzaldehyde
3-Bromobenzaldehyde
4-Bromoanisole
>99
>99
>99
90
4
5
6
3-Bromoanisole
7
4-Bromotoluene
>99
>99
78
8
2-Bromotoluene
9
4-Bromoaniline
10
11
12
13
14
15
16
17
18
2-Bromobenzonitrile
3,5-Bis(trifluoromethyl)bromobenzene
1-Bromo-2,4,6-triisopropylbenzene
1-Bromo 4-nitrobenzene
4-Iodoacetophenone
4-Iodotoluene
>99
>99
<5
Entry
Cycle
Conversion (%)b
>99
>99
>99
>99
14
1
2
3
4
5
1
2
3
4
5
90
90
88
88
88
Methyl 4-iodobenzoate
2-Chlorobenzaldehyde
4-Chlorobenzaldehyde
33
aReaction conditions: aryl halide (1.01mmol), phenylboronic acid
(1mmol), K2CO3 (1.12 mmol), solvent (1.2mL), HNT-IL/Pd (1mol%).
bDetermined by 1H-NMR.
aReaction conditions: aryl halide (1.01 mmol), phenylboronic acid
(1mmol), K2CO3 (1.12mmol), solvent (1.2ml), HNT-IL/Pd (1mol%).
1
bDetermined by H-NMR.
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Appl. Organometal. Chem. 2014, 28, 234–238

Green conditions for the Suzuki reaction under microwave irradiation
Table 5. Suzuki cross-coupling reaction of phenylboronic acid with
various halides under optimized reaction conditions under micro-
wave irradiationa
catalyst, associated with the advantages that microwave
irradiation brought to the Suzuki reaction, in terms of energy
saving, time and yield, contributes to a more efficient green
process with less waste production. Recycling studies were
briefly investigated, and HNT-SILLP showed good recyclability
in such catalytic systems.
Experimental
General Data
Entry
Ar-X
Conversion (%)b
Microwave-assisted syntheses were carried out with a CEM
DISCOVER monomode system in a closed vessel. 1H NMR spectra
were recorded at 250 MHz in CDCl3 solution at room temperature
on a Bruker AC-E Series 300 spectrometer. Palladium chloride,
aryl halide and all other chemicals were purchased from Sigma-
Aldrich and used without further purification. HNT-Pd catalyst
was synthesized according to published methods.[20]
1
2
3
4-Bromoacetophenone
4-Bromobenzaldehyde
3-Bromoanisole
>99
>99
90
aReaction conditions: aryl halide (1.01 mmol), phenylboronic acid
(1 mmol), K2CO3 (1.12 mmol), solvent (1.2ml), HNT-IL/Pd (1mol%).
bDetermined by 1H-NMR.
Typical Procedure for the Suzuki Reaction via microwave
irradiation
five cycles while retaining the same activity and selectivity as
well as without, presumably, loss of the active Pd species. It is
known that when the SILLP/Pd catalyst was employed at high
temperature no leaching of the catalyst was detected upon
recycling.[24]
The absence of leaching in Pd catalysts immobilized on to gel-
supported ionic-liquid phase has been ascribed to a ‘release and
catch’ mechanism.[25] It has been proposed that during Suzuki
coupling palladium is dissolved in solution (leaching), then after
completion of the process palladium is redeposited on to the
support and its full and efficient recovery can be achieved if the
redeposition is complete at the end of the reaction.[25c] As can
be seen in Table 4, the reaction yield ranged from 90% to 88%.
We can therefore conclude that microwave irradiation did not
destroy the HNT-Pd catalyst.
In order to use more green conditions, we checked if a lesser
quantity of HNT-IL/Pd catalyst could be employed without
affecting the yield, as well as the selectivity of the reaction. With
this idea in mind, we carried out a set of reactions using catalyst
HNT-IL/Pd in 0.1 mol% (Table 5). It is interesting to note that
yields were comparable to those obtained using HNT-IL/Pd in
1 mol%. These results represent, in our opinion, a clear advantage
because it is possible to employ only a small amount of heteroge-
neous catalytic material (5 mg).
HNT-Pd catalyst (1% or 0.1 mol%), phenylboronic acid (65 mg,
0.547 mmol), K2CO3 (84 mg, 0.615 mmol), aryl bromide (0.55 mmol),
ethanol (0.6 ml) and water (0.6 ml) were placed in a micro-
wave test tube provided with a cap The mixture was inserted
into microwave apparatus at a temperature of 120 °C and
14 W power, under constant stirring for 10 min; the solvent
was then removed under reduced pressure and the residue
was checked by 1H-NMR to calculate conversion.
Recyclability of the Catalyst
HNT-IL/Pd catalyst (1mol%), phenylboronic acid (65mg, 0.547mmol),
K2CO3 (84 mg, 0.615 mmol), 3-bromoanisole (0.55 mmol), ethanol
(0.6 ml) and water (0.6 ml) were placed in a microwave test tube
provided with a cap. The mixture was inserted into the MW apparatus
at a temperature of 120 °C and 14 W power, under constant stirring
for 10 min. The reaction mixture was then centrifuged and the
liquid mixture was decanted; the residual solid was washed with
CH2Cl2, water and Et2O. HNT-IL/Pd was dried and reused.
Acknowledgments
This work was financially supported by the University of Palermo
and PRIN 2010–2011 (prot. 2010329WPF).
References
[1] a) R. Chinchilla, C. Najera, Chem. Rev. 2007, 107, 874–922. b) I. P. A.
Beletskaya, V. Cheprakov, Chem. Rev. 2000, 100, 3009–3066.
c) V. Ritleng, C. Sirlin, M. Pfeffer, Chem. Rev. 2002, 102, 1731–1769.
[2] a) J. P. Corbet, G. Mignani, Chem. Rev. 2006, 106, 2651–2710. b) N. T. S.
Phan, M. Van Der Sluys, C. W. Jones, Adv. Synth. Catal. 2006, 348,
609–679. c) L. Yin, J. Liebscher, Chem. Rev. 2007, 107, 133–173.
d) F. Alonso, I. P. Beletskaya, M. Yus, Tetrahedron 2008, 64, 3047–3101.
[3] R. Capdeville, E. Buchdunger, J. Zimmermann, A. Matter, Nat. Rev.
Drug Discov. 2002, 1, 493–502.
[4] a) K. L. McPhail, D. E. A. Rivett, D. E. Lack, M. T. Davies-Coleman,
Tetrahedron 2000, 56, 9391–9396. b) Y. Q. Long, X. H. Jiang,
R. Dayam, T. Sachez, R. Shoemaker, S. Sei, N. J. Neamati, Med. Chem.
2004, 47, 2561–2573. c) S. S. Moleele, J. P. Michael, C. B. de Koning,
Tetrahedron 2006, 62, 2831–2844.
Conclusions
In this work we have reported data on the Suzuki reaction in
heterogeneous phase using as catalyst a new HNT-supported
ionic liquid-like phase (HNT-SILLP) and microwave irradiation.
The contributions of solvent, time, base and catalyst amounts
were investigated. The results show that microwave irradiation
improves yield and conversion in the Suzuki reaction in compar-
ison to the traditional heating previously reported by our group.
In addition, it is remarkable to note that the HNT-IL/Pd catalyst
(support 1 mol%, Pd 7 × 10À3 mg) appears to be more efficient
than those we used previously on a silica support (support
1 mol%, Pd 0.10 mg) despite lesser amounts of Pd on its surface.
This latter aspect, with only a small amount of Pd used as the
[5] M. Kertesz, C. H. Choi, S. Yang, Chem. Rev. 2005, 105, 3448–3481.
[6] S. Kaye, J. M. Fox, F. A. Hicks, S. L. Buchwald, Adv. Synth. Catal. 2001,
343, 789–794.
Appl. Organometal. Chem. 2014, 28, 234–238
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

M. Massaro et al.
[7] M. Kertesz, C. H. Choi, S. Yang, Chem. Rev. 2005, 105,
3448–3481.
[15] S. Barrientos-Ramirez, G. Montes de Oca-Ramirez, E. V. Ramos-
Fernandez, A. Sepùlveda-Escribano, M. M. Pastor-Blas, A. Gonzàlez-
Montiel, Appl. Catal. A 2011, 406, 22–33.
[8] D. G. Hall, Boronic Acids, Wiley-VCH, Weinheim, 2005, pp. 1–99.
[9] a) L. Pu, Chem. Rev. 1998, 98, 2405–2494. b) L. F. Tietze, G.
Kettschau, U. Heuschert, G. Nordmann, Chem. Eur. J. 2001, 7,
368–373. c) A. F. Littke, G. C. Fu, Angew. Chem. Int. Ed. 2002,
41, 4176–4211.
[16] D. Zhang, W. Huo, J. Wang, T. Li, X. Cheng, J. Li, A. Zhang, J. Appl.
Polym. Sci. 2012, 126, 1580–1584.
[17] a) R. K. Sharma, D. Rawat, Inorg. Chem. Commun. 2012, 17, 58–63.
b) R. K. Sharma, C. Sharma, I. T. Sidhwani, J. Chem. Educ. 2011, 88,
85–87. c) R. K. Sharma, S. Gulati, S. Sachdeva, Green Chem. Lett. Rev.
2012, 5, 83–87. d) R. K. Sharma, G. Ahuja, I. T. Sidhwani, Green Chem. Lett.
Rev. 2009, 2, 101–105. e) Y. Liu, C. Khemtong, J. Hu, Chem. Commun.
2004, 10, 398–399. f) K. Hayashi, S. Kim, Y. Kono, M. Tamura, M. Chiba,
Tetrahedron Lett. 2006, 47, 171–174. g) R. K. Leadbeater, N. E. Mack,
T. L. Kormos, Tetrahedron Lett. 2006, 47, 217–220. h) F. Chanthavong,
N. E. Leadbeater, Tetrahedron Lett. 2006, 47, 1909–1912.
[18] a) N. E. Leadbeater, M. Marco, J. Org. Chem. 2003, 68, 5660–5667.
b) N. E. Leadbeater, Chem. Commun. 2005, 23, 2881–2902.
[19] K. L. dos Santos Castroa, P. G. de Limaa, S. M. Leandro, L. S. M. e
Miranda, O. M. A. Rodrigo, R. O. M. A. de Souza, Tetrahedron Lett.
2011, 52, 4168–4171.
[10] a) D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606–
5655. b) E. A. B. Kantchev, C. J. O Brien, M. G. Organ, Angew. Chem.
2007, 119, 2824; Angew. Chem. Int. Ed. 2007, 46, 2768–2813.
c) J. W. Ruan, O. Saidi, J. A. Iggo, J. L. Xiao, J. Am. Chem. Soc. 2008,
130, 10510–10511. d) W. A. Herrmann, C.-P. Reisinger, M. J. Spiegler,
Organomet. Chem. 1998, 557, 93–96. e) W. A. Herrmann, Angew.
Chem. 2002, 114, 1342; Angew. Chem. Int. Ed. 2002, 41, 1290–1309.
f) O. Navarro, R. A. Kelly III, S. P. Nolan, J. Am. Chem. Soc. 2003, 125,
16194–16195. g) G. Altenhoff, R. Goddard, C. W. Lehmann, F. Glorius,
J. Am. Chem. Soc. 2004, 126, 15195–15201. h) A. E. Wang, J. H. Xie,
L. X. Wang, Q. L. Zhou, Tetrahedron 2005, 61, 259–266. i) H. Lv,
L. Zhu, Y.-Q. Tang, J.-M. Lu, Appl. Organometal. Chem. 2013,
doi:10.1002/aoc.3053.
[20] M. Massaro, S. Riela, G. Cavallaro, M. Gruttadauria, S. Milioto, R. Noto,
[11] a) A. N. Marziale, S. H. Faul, T. Reiner, S. Schneider, J. Eppinger, Green
Chem. 2010, 12, 35–38. b) M.-T. Chen, C.-A. Huang, C.-T. Chen, Eur. J.
Inorg. Chem. 2008, 20, 3142–3150.
G. Lazzara, J. Organometal. Chem. 2014, 749, 410–415.
[21] J. A. Tyburczy, D. K. Fisler, Mineral Physics and Crystallography: A
Handbook of Physical Constants, American Geophysical Union,
Washington, DC, 1995, pp. 185–209.
[22] M. Gruttadauria, L. F. Liotta, A. M. P. Salvo, F. Giacalone, V. La Parola,
C. Aprile, R. Noto, Adv. Synth. Catal. 2011, 353, 2119–2130.
[23] A. R. Hajipour, K. Karami, G. Tavakoli, Appl. Organometal. Chem. 2012,
26, 401–405.
[12] a) A. Corma, H. Garcia, A. Primo, J. Catal. 2007, 251, 39–48. b) B. M.
Choudary, S. Madhi, N. S. Chowdari, J. Am. Chem. Soc. 2002, 124,
14127–14136. c) G. Wei, W. Q. Zhang, F. Wen, Y. Wang, M. C. Zhang,
J. Phys. Chem. C 2008, 112, 10827–10832. d) N. Jamwal, M. Gupta, S.
Paul, Green Chem. 2008, 10, 999–1003. e) L. Li, J. L. Shi, J. N. Yan,
Chem. Commun. 2004, 10, 1990–1991. f) M. J. Gronnow, R. Luque,
D. J. Macquarrie, J. H. Clark, Green Chem. 2005, 7, 552–557. g) A.
Schatz, T. R. Long, R. N. Grass, W. J. Stark, P. R. Hanson, O. Reiser,
Adv. Funct. Mater. 2010, 20, 4323–4328.
[13] M. Gruttadauria, F. Giacalone, R. Noto, Green Chem. 2013, 15,
2608–2618.
[14] G. S. Machado, K. A. D. de Freitas Castro, F. Wypych, S. Nakagaki,
J. Molec. Catal. A 2008, 283, 99–107.
[24] M. I. Burguete, E. Garcìa-Verdugo, I. Garcia-Villar, F. Gelat, P. Licence,
S. V. Luis, V. Sans, J. Catal. 2010, 269, 150–160.
[25] a) Z. Niu, Q. Peng, Z. Zhuang, W. He, Y. Li, Chem. Eur. J. 2012, 18,
9813–9817. b) M. I. Burguete, E. Garcia-Verdugo, I. Garcia-Villar, F.
Gelat, P. Licence, S. V. Luis, V. Sans, J. Catal. 2010, 269, 150–160.
c) K. Kçhler, R. G. Heidenreich, S. S. Soomro, S. S. Prçckl, Adv. Synth.
Catal. 2008, 350, 2930–2936. d) F. Zhao, M. Shirai, Y. Ikushima, M.
Arai, J. Mol. Catal. A 2002, 180, 211–219.
wileyonlinelibrary.com/journal/aoc
Copyright © 2014 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2014, 28, 234–238