Arylation of alkynes over hydrotalcite docked Rh-m-TPPTC complex

Article abstract of DOI:10.1016/j.cattod.2014.07.004

Rh-m-TPPTC complex was successful immobilized onto a hydrotalcite Zn-Al to convert selectively in aqueous media both the symmetric and nonsymmetric alkynes into functionalized alkenes, with boronic acids. The complex preserved its activity after the ionic exchange, leading to excellent results (～87%) for the symmetric alkynes and also for the non-symmetrical alkynes (up to 99%).

Full text of DOI:10.1016/j.cattod.2014.07.004

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Arylation of alkynes over hydrotalcite docked Rh-m-TPPTC complex
Florentina Neat¸ua,b, Ma˘da˘lina Ciobanua, Laura E. S¸ tofleab, Ligia Frunza˘ b,
Vasile I. Pârvulescua,∗, Véronique Micheletc,∗
a University of Bucharest, Department of Organic Chemistry, Biochemistry and Catalysis, 4-12 Regina Elisabeta Blvd., 030016 Bucharest, Romania
b National Institute of Materials Physics, Laboratory of Optical Processes in Nanostructured Materials, 105Bis Atomistilor Street, PO Box MG7 Magurele,
Bucharest, Romania
c PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 75005, Paris, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Rh-m-TPPTC complex was successful immobilized onto a hydrotalcite Zn-Al to convert selectively in
aqueous media both the symmetric and nonsymmetric alkynes into functionalized alkenes, with boronic
acids. The complex preserved its activity after the ionic exchange, leading to excellent results (∼87%) for
the symmetric alkynes and also for the non-symmetrical alkynes (up to 99%).
Received 20 February 2014
Received in revised form 26 June 2014
Accepted 4 July 2014
Available online xxx
© 2014 Elsevier B.V. All rights reserved.
Keywords:
Alkynes
Arylboronic acid
Heterogeneous catalysis
Water
Rhodium
1. Introduction
the metal recycling and the easy product/catalyst separation [9].
The literature reported in the 1980s the use of organometal-
Since Miyaura has for the first time reported the addition of
aryl- and alkenylboronic acids to ␣,␤-unsaturated ketones cat-
alyzed by a rhodium-phosphine complex in an aqueous solvent,
organoboron compounds have emerged as reagents of choice
in various transition-metal-catalyzed reactions [1]. The interest
to this development was further extended for the addition of
organoboronic acids to various unsaturated substrates [2,3] includ-
ing terminal olefins such as styrenes and vinylpyridines [4]. A
special attention was focused also onto addition of organoboron
acid to alkynes, a reaction that was discovered by Hayashi’s
group [5] and now catalyzed by various transition metals [6].
The investigation of such reactions in water enlarged the val-
orisation possibilities but few reports were described so far [7].
Indeed, even though working in water allies economic, environ-
mental and reaction efficiency advantages [8], the use of water
requires, however, the presence of cooperative catalysts that
should be able to combine the high catalytic efficiency with
lic systems with water-soluble ligands. TPPTS (trisodium salt
of 3,3ꢀ,3ꢀꢀ-phosphane triylbenzenesulfonic acid) was one of the
most popular water soluble ligands and it was widely used in
a variety of transition metal-catalyzed reactions [10,11], such as
palladium-catalyzed cross-coupling and nucleophilic substitutions
[12], nickel-catalyzed cross-couplings [13], palladium, rhodium or
nickel-catalyzed ene-reaction [14] and palladium and platinum-
catalyzed car-boalkoxycyclization [15]. However, since hydrophilic
sulfonated phosphane TPPTS and analogues are ineffective sys-
tems [7,11], new ligands [16] such as m-TPPTC (trilithium salt of
3,3ꢀ,3ꢀꢀ-phosphane-triylbenzenecarboxylic acid) were designed to
promote the arylation of alkynes in pure water or in a biphasic sol-
vent [7b–d]. Heterogeneization of such water cooperative catalysts
may generate even more efficient catalysts [17].
In this approach, and following our endeavor in heterogeneous
catalysis [18], we have performed for the first time the addition of
arylboronic acids to alkynes in the presence of a heterogeneous
catalyst. More specifically, a Rh-m-TPPTC complex was success-
fully immobilized onto a layered double hydroxide Zn-Al (LDH)
(Scheme 1) to convert selectively in aqueous media both the sym-
metric and nonsymmetric alkynes into functionalized alkenes, with
boronic acids.
∗
Corresponding authors. Tel.: +40 21 4100241; fax: +40 21 4100241.
E-mail addresses: vasile.parvulescu@g.unibuc.ro (V.I. Pârvulescu),
veronique.michelet@chimie-paristech.fr (V. Michelet).
http://dx.doi.org/10.1016/j.cattod.2014.07.004
0920-5861/© 2014 Elsevier B.V. All rights reserved.
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Scheme 1. m-TPPTC and TPPTS ligand structure and immobilized of Rh-m-TPPTC complex onto layered double hydroxide Zn-Al (LDH); (color code: black = C, blue = H, red = O,
grey = Li, green = Cl, pink = Rh).
Brunauer–Emmett–Teller (BET) method in the p/p0 (low case,
according to IUPAC) range of 0.05–0.35. Pore size distribution
curves were calculated from the adsorption branch of the isotherms
with the Barrett–Joyner–Halenda (BJH) method, and pore sizes
were obtained from the peak positions of the distribution curves.
Both Rh-catalysts and LDH support were characterized by powder
X-ray diffraction (XRD) using a Siemens D5000 X-ray diffractome-
2. Experimental
2.1. Catalyst preparation
Two types of catalysts were prepared. Rh-m-TPPTC and
Rh-TPPTS complexes were immobilized onto layered double
hydroxides (LDH) containing Zn and Al. The heterogeneiza-
tion of Rh-m-TPPTC complex on LDH followed the same
procedure as for the Rh-TPPTS complex, as described else-
where [18a]. The Zn3AlCl LDH was prepared following methods
described in the literature [19]. The ionic exchange capacity of
˚
ter with nickel filtered Cu K␣ radiation (ꢀ = 1.5418 A) at a scanning
rate of 0.1◦·min−1 in the 2ꢁ range of 10–80◦. X-ray photoelectron
spectroscopy (XPS) was performed in an analysis chamber (Specs)
by using a monochromatized Al K␣1 X-ray source (photon energy
1486.74 eV) on powders pressed on carbon tapes by using ultrason-
ically cleaned tools. Electrons are collected in normal emission and
analyzed by a 150 mm radius Phoibos electron analyzer operating
in large area mode with pass energy of 30 eV. The estimated exper-
imental resolution in these conditions is in the range of 0.90 eV
Gaussian width (FWHM), with a total width (including the core
hole width) of 1.15 eV obtained on Au 4f7/2 core levels [20]. A
flood gun with acceleration voltage of 1 eV and electron current
of 0.1 mA was employed to ensure the sample neutralization. It
has been demonstrated that this flood gun parameters and exper-
imental arrangements is effective in neutralizing charging effects
on highly insulating thin films [21] and also on insulating powders
pressed on carbon tapes, as in the actual case [22]. The XPS data are
analyzed with normalized Voigt profiles, which are convolutions of
lorentzian and gaussian lineshapes [22]. The inelastic background
is simulated with integrals of Voigt lineshapes, derived also from
Ref. [23]. For a doublet, when the spin-orbit splitting approaches
the range of ionization energy or workfunction of the material,
the lorentzian core level widths are allowed to vary (e.g. from
Rh 3d5/2 to Rh 3d3/2) to account for the opening of Coster–Kronig
decay channels yielding to a lower core hole lifetime of the state
with higher binding energy [24]. The gaussian width was kept the
same for all components. Chemical composition of the catalysts
was determined by Atomic Emission Spectroscopy (ICP-AES) using
a Plasma 40, Perkin-Elmer equipment after appropriate dissolution
[Zn0.76Al0.24(OH)2]Cl0.24·0.8H2O] (Zn3AlCl) was 1.1 meq g−1
.
2.1.1. Rh-ligand complex synthesis:
The complex Rh-m-TPPTC and Rh-TPPTS were prepared under
inert atmosphere starting from [Rh(cod)Cl]2 precursor (0.25 mmol
of metal) and (1 mmol) m-TPPTC and TPPTS ligand, respectively in
50 mL deionizated water (the solution was stirred for 12 h).
2.1.2. Heterogeneization of Rh-ligand complex:
The preparation of catalysts Rh-m-TPPTC and Rh-TPPTS sup-
ported on LDH were synthesized by ionic exchange method. To
the mixture containing the Rh-ligand complex described above,
under inert atmosphere, 1 g of Zn3AlCl LDH was added. After 24 h
of stirring, the solution was filtered and the solid was washed with
deionized water, and dried under vacuum at room temperature for
16 h.
2.2. Catalysts characterization
The characterization of the catalysts was carried out using
several techniques. N2 adsorption–desorption isotherms of the
LDH support and the Rh-catalysts were measured at −196 ◦C
with a Micromeritics ASAP 2020. Prior to measurements, the
samples were degassed at 150 ◦C under vacuum for more
than 6 h. The specific surface areas were evaluated with the
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Fig. 1. PXRD pattern of Zn3Al-LDH ionic exchanged with Rh-m-TPPTC complex.
of the solid samples. 31P NMR analyses were performed on a Bruker
500 MHz NMR spectrometer. DRIFTs investigation of the materi-
als were realized with a Nicolet 4700 spectrometer (400 scans,
500–4000 cm−1 scan range, 4 cm−1 resolution).
on our previous reports [17a,18g], we can conclude that the basal
spacing 16.03 A of the (0 0 3) refection plan, observed in the new
˚
formed phase, is enough to accommodate only one molecule of
ligand (m-TPPTC) and not the whole Rh-complex. Probably, due
to the high dimension of the complex, the ionic exchange had
place on the external surface or better at the edge of the LDH
(Scheme 1). However, the low intensity of the peaks assigned to
the new phase formed containing Rh-m-TPPTC complex indicates
a relatively small contribution of this phase and a low extent of
ion-exchange of Rh-complex for the inorganic anions. The chemical
composition and the textural characterization of the investigated
catalysts revealed an important decrease of the surface area. The
surface area of the docked complexes represented ca. 50% of that
of the initial LDH (Table 2). This decrease provides additional
evidences on the ionic exchange of Rh-m-TPPTC and Rh-TPPTS com-
plexes inside the LDH.
Table 3 compiles the XPS binding energies of the constitutive
elements (Al 2p, Zn 2p, P2p, Rh3d [5]) and the atomic XPS Rh:Zn
ratios. No change of the binding energies of Al 2p and Zn 2p after
the ionic exchange with Rh-m-TPPTC or Rh-TPPTS complexes was
observed, meaning that the oxidation state of the constitutive ele-
ments was not altered by ionic exchange.
2.3. Catalytic test
Typical experiments were carried out by adding, at room tem-
perature, to a reaction mixture of arylboronic acid (2.5 equiv)
and 30 mg heterogeneous Rh-m-TPPTC/LDH catalyst 1 equivalent
alkyne and the solvent (water or water/toluene (1/1), 2.5 M). The
mixture was heated at 100 ◦C under stirring, for 3 h. After cooling
the reaction mixture, the catalyst was centrifuged and separated
from the mixture, and the resulted product was extracted with
toluene (two times) and dichloromethane (two times). The resulted
light yellow oil did not require any further purification. The 1H NMR
and 13C NMR analyses (performed on a Bruker AV 300 instrument)
and GS–MS analyses (Varian Trace GC Ultra – DSQ instrument) of
the products 3a–f and 4a–h were identical at those published in
the literature [7c,d].
3. Results and discussions
Fig. 2 presents XPS spectra of the Rh precursor ([Rh(cod)Cl]2)
and of Rh-m-TPPTC/LDH. According to previous findings, the bind-
ing energy of Rh 3d in ([Rh(cod)Cl]2) corresponds to the oxidation
state of Rh(I) [25]. After the complexation of the ([Rh(cod)Cl]2) com-
plex with phosphine, the XPS spectrum shows a shift of the binding
energy of the Rh 3d level to lower binding energies and an asym-
metry assigned to two components. The band at 306.0 eV may be
assigned to the new Rh–P bond in the Rh-m-TPPTC complex, while
3.1. Catalysts characterization
The XRD patterns of Rh-TPPTS/LDH were already reported in
other work [17a,18a]. As in the case of Rh-TPPTS/LDH, the XRD
analysis of Rh-m-TPPTC-LDH shows patterns indicating the partial
insertion of the ligand between the layers of the double hydroxide.
Patterns shown in Fig. 1 indicate both the well-ordered layered
structure of the initial LDH and of the LDH ionic exchanged with
the Rh-m-TPPTC complex. After ionic exchange can be observed
a main phase of the initial Zn3Al-LDH, which contain Cl− between
the layers, but also another phase with the three harmonics located
at 2ꢁ 5.5◦ (0 0 3), ∼11◦ (0 0 6) and 16.7◦ (0 0 9). This new phase
corresponds to a higher c parameter of the lattice (Table 1) rep-
resenting an evidence of the enlargement of the distance between
layers, caused by the docked complex. In their work, Chen et al.
[17b] are demonstrating that the insertion of one molecule of TPPTS
ligand between the layers of a hydrotalcite will increase the d0 0 3
Table 1
Lattice parameters a and c resulted from the PXRD pattern of the Zn3Al-LDH fresh
and after ionic exchange.
LDH initial (Å)
Rh-m-TPPTC/LDH (Å)
d0 0 3
d0 0 6
d0 0 9
7.79
3.91
2.62
23.48
1.55
3.11
16.03
8.04
5.31
48.04
1.55
3.11
c (lattice parameter)
d1 1 0
a (lattice parameter)
˚
basal spacing to a value ∼16 A. Based on these observations and
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Table 2
The chemical composition and the surface areas of the investigated catalysts.
Catalyst
Chemical composition
Zn:Al ratio
Specific surface area, m2 g−1
Rh:Al ratio
Rh, wt%
TPPTS or m-TPPTC wt%
LDH
3
3
3
–
0.43
0.42
–
2.51
2.45
–
41.9
29.5
94
51
55
Rh/TPPTS LDH
Rh/m-TPPTC LDH
Table 3
XPS binding energies and atomic XPS Rh:Zn ratios.
Catalyst
XPS binding energies, eV
XPS composition
Rh:Zn ratio
Al2p
Zn2p3
P2p
Rh3d
Rh3d3/2
Rh3d5/2
LDH
74.1
–
74.2
1021.7
–
1021.6
–
–
–
–
–
–
[Rh(COD)Cl]2
Rh-m-TPPTC/LDH
313.1
310.8
312.8
308.4
306.0
308.0
132.5
0.055
Table 4
DRIFT analyses were recorded for both LDH and Rh-m-
TPPTC/LDH materials (Fig. 3). No significant difference could be
observed between the two spectra, except an increase in the range
1400–1470 cm−1, which could be assigned to the phenyl group of
the m-TPPTC ligand.
ICP-AES analysis of the Rh-m-TPPTC or Rh-TPPTS supported on
LDH indicated a similar Rh content. The TPPTS:Rh (wt%) ratio was
found of 2.87 that is in agreement with the structure of the expected
complex [27].
31P NMR of the m-TPPTC the Rh-m-TPPTC complex in D2O, and 31P MAS NMR the
ionic-exchange Rh-m-TPPTC/LDH.
No
Sample
Chemical shift
1
2
3
m-TPPTC
RhCl(m-TPPTC)3
Rh-m-TPPTC/LDH
−5.6
30.2
29.9
that at 308.0 eV to the remanent Rh–Cl bond. The immobilization
of the complex on LDH caused no change in the XPS spectrum. The
binding energy of P 2p level at 132.5 eV confirms the preservation
of the phosphorous oxidation state during the immobilization pro-
cedure of the complex (Fig. 2b). Similar spectra were recorded for
the Rh-TPPTS/LDH complex [17a].
3.2. Catalytic tests
Both catalysts Rh-m-TPPTC/LDH and Rh-TPPTS/LDH were tested
in the addition of boronic acids to different alkynes (symmetric or
non-symmetric). As it was anticipated [7c.d], the Rh-TPPTS/LDH
catalyst shows no activity for this addition. We had indeed observed
a lower activity (and selectivity) of the Rh/TPPTS catalyst com-
pared to the Rh-m-TPPTC complex under homogeneous conditions.
The heterogeneization of such systems enhances this phenomenon.
Table 5 presents the results of the addition of different boronic
acids to the symmetric alkyne (4-octyne) in the presence of Rh-m-
TPPTC/LDH. Following our previous findings on the use of m-TPPTC
ligand for such transformation under homogeneous conditions
[7c,d], we chose a biphasic system (toluene/water) as the reaction
medium. Pleasingly the supported catalyst was found to be effective
31P NMR was used to investigate the complexation of the phos-
phine ligand with ([Rh(cod)Cl]2). Table 4 compiles the 31P chemical
shift for the m-TPPTC ligand, the Rh-m-TPPTC complex and the
ionic-exchanged Rh-m-TPPTC/LDH. The spectra were recorded con-
sidering H3PO4 as standard. The spectrum of m-TPPTC shows
resonance at −5.6 ppm [16a], while that of the Rh-m-TPPTC com-
plex at 30.2 ppm. These results are in agreement with the reported
literature data [26]. The ionic exchange led to no significant chem-
ical shift of the 31P nuclei, proving once more that the Rh-complex
is not affected by the immobilization procedure.
Fig. 2. Rh 3d (a) and P2p (b) XPS spectra of Rh-m-TPPTC/LDH catalyst.
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Table 5
Addition of arylboronic acids to 4-octyne (in the presence of Rh-m-TPPTC/LDH catalyst).
Entrya
ArB(OH)2
Solvent
Alkene/ dimer ratio
Yielda (Conv.) [%]
1
2
3
4
5
6
7
2a
2b
2c
2d
2e
2f
H2O/toluene
H2O/toluene
H2O/toluene
H2O/toluene
H2O/toluene
H2O/toluene
H2O
96/4
96/4
96/4
96/4
96/4
96/4
88/12
87 (1 0 0)
85 (1 0 0)
87 (1 0 0)
84 (1 0 0)
86 (1 0 0)
86 (1 0 0)
85 (1 0 0)
2d
a
Isolated yield.

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Fig. 3. DRIFTs spectra of the LDH and Rh-m-TPPTC/LDH.
and isolated yields in the range 84–87% were obtained irrespective
of the boronic acids substituent (Table 5, entries 1–6). The reaction
conditions were compatible with electron-withdrawing, electron-
donating or sterically hindered groups on the boronic acid. As
anticipated [7c,d], working in pure water led to an increased yield
of dimer, which should be associated to the hydrophobicity of the
resulted alkene (Table 5, entry 7). The formed alkenes (hydrophobic
molecules) often generate emulsion clusters in water, favoring the
reaction between two alkenes or more thus leading to secondary
products, like dimers. Carrying the reactions out in a biphasic
mixture (toluene:water 1:1) therefore diminished the formation
of side products. Under these conditions the alkene/dimer ratio
was increased from 88/12 to 96/4 irrespective of the investigated
boronic acid partner (Table 5, entries 4, 7).
We then turned our attention to the arylation of other
alkynes such as non-symmetrical ones (Table 6). The reaction of
phenylboronic 2a and 2-methoxy-phenyl boronic acids 2d with
the non-symmetric alkynes hex-1-ynylbenzene 1b and prop-1-
ynylbenzene 1c performed only with moderate yields (Table 5,
entries 1–4). Moreover, the dimer formation became a highly com-
petitive process in the case of 1c (Table 6, entries 2, 4 and 6). The
lower steric hindrance of the alkyne 1c compared to 1b may account
for this observation. When the steric hindrance of the boronic acid
was increased, such as for 2f, the high selectivity of the reaction
towards the formation of the desired alkene 4 h was recovered
(Table 6, entry 8). In the case of alkyne 1b, the naphthylboronic acid
2f and trifluoromethyl phenyl acid 2e were good partners (Table 6,
entries 5 and 7). The naphthylboronic acid 2f afforded only the for-
mation of the alkene (Table 6, entries 7, 8) most presumably due
to its steric hindrance, while the trifluoromethyl phenyl boronic
acid 2e allowed the formation of the corresponding dimer (Table 6,
entry 6).
Table 7 presents the results for the first four runs using substrate
1a with the arylboronic 2a and 2f acids in the presence of Rh-m-
Table 7
Recycling tests for the substrate 1a with 2a and 2f arylboronic acid in the presence
of the Rh-m-TPPTC/LDH catalyst (3 h reaction time).
Alkyne (1) and boronic acid (2)
Run 1
Run 2
Run 3
Run 4
1a with 2a
1a with 2f
87a (1 0 0)b
86 (1 0 0)
87 (1 0 0)
86 (1 0 0)
85 (99)
85 (98)
84 (97)
85 (98)
a
Isolated yield [%].
Conversion [%].
b
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TPPTC/LDH catalyst after 3 h. The supported catalytic system can
easily be separated by centrifugation under ambient conditions.
The recovered catalyst (by simple decantation) was simply added
to the next reaction mixture without any additional treatment. The
supported catalysts were recycled with a slightly loss of conversion
and yield after the second run (Table 7). The absence of any leaching
was also confirmed by the ICP-AES analysis of the reaction products.
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4. Conclusions
The heterogeneization of Rh-m-TPPTC complex used in homoge-
neous catalysis for the 1,4-addition of arylboronic acids to alkynes
was successfully achieved. The complex preserved its activity after
the ionic exchange, leading to excellent results (∼87%) for the sym-
metric alkynes. As in the case of homogeneous conditions, the
biphasic system (water/toluene) was found to be highly impor-
tant for the selectivity of the reaction. Good to excellent activity of
the Rh-m-TPPTC/LDH was also observed for the non-symmetrical
alkynes (up to 99%), with a high dependence of the steric hindrance
regarding the selectivity of the reaction. Recycling of the catalyst
was successfully performed (up to four runs) without evidence of
leaching.
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Acknowledgments
This work was supported by a grant of the Romanian Ministry of
Education, CNCS– UEFISCDI, project number PN-II-RU-PD-2012-3–
0295, by the French Ministère de l’Enseignement Supérieur et de la
Recherche (MESR) and Centre National de la Recherche Scientifique
(CNRS). Laura E. S¸ toflea was funded by the NIMP Kernel Programme
45N/2009.
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