Cooperative effects of lanthanides when associated with palladium in novel, 3D Pd/Ln coordination polymers. Sustainable applications as water-stable, heterogeneous catalysts in carbon-carbon cross-coupling reactions

Article abstract of DOI:10.1016/j.apcata.2015.11.044

Three novel porous heterobimetallic coordination polymers, [Ln₂Pd₃(BPDC)₂(HBPDC)₂(μ₂-O)Cl₄(H₂O)₆·nH₂O]_m (Ln = Pr, n = 5 (1), Ln = Gd, n = 4 (2), and Ln = Tb, n = 4 (3)), were readily prepared by combining Pd(II) and Ln(III) with 2,2′-bipyridine-4,4′-dicarboxylic acid (H₂BPDC) as a heteroleptic ligand, under hydrothermal conditions, and structurally characterized by means of single-crystal X-ray diffraction, FT-IR, powder X-ray diffraction, elemental analysis and thermogravimetric (TG) techniques. Single-crystal X-ray diffraction examination showed that 1-3 have similar 3D frameworks, connected via hydrogen bonding interactions, and consisting of three distinct types of building blocks: Pd(BPDC)Cl₂, Pd(HBPDC)₂ and a Ln dimer (Ln₂O₁₅). The new isostructural, air and water stable coordination polymers, resulting from association of lanthanides with palladium, exhibited superior but distinct capabilities as eco-friendly heterogeneous catalysts in Suzuki-Miyaura, Heck and Sonogashira cross-couplings, under green reaction conditions. Supramolecular, solid catalysts 1-3 have been recovered quantitatively from the reaction mixtures by simple filtration. Also importantly, their sustainability, utility and cost-effectiveness have been demonstrated by recycling experiments with catalyst 1 in Suzuki-Miyaura, proceeding practically without loss of activity after four runs.

Full text of DOI:10.1016/j.apcata.2015.11.044

Applied Catalysis A: General 511 (2016) 1–10
Contents lists available at ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Cooperative effects of lanthanides when associated with palladium in
novel, 3D Pd/Ln coordination polymers. Sustainable applications as
water-stable, heterogeneous catalysts in carbon–carbon
cross-coupling reactions
a
a
a
a
a
a
Lixin You , Wenhui Zong , Gang Xiong , Fu Ding , Shuju Wang , Baoyi Ren ,
b
b,∗
a,∗
Ileana Dragutan , Valerian Dragutan , Yaguang Sun
The Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, Shenyang University of Chemical Technology, Shenyang, PR China
Institute of Organic Chemistry, Romanian Academy, Bucharest, Romania
a
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 September 2015
Received in revised form
Three novel porous heterobimetallic coordination polymers, [Ln Pd (BPDC) (HBPDC) (ꢀ -
2
3
2
2
2
O)Cl4(H2O)6·nH2O]m (Ln = Pr, n = 5 (1), Ln = Gd, n = 4 (2), and Ln = Tb, n = 4 (3)), were readily prepared
ꢀ
ꢀ
by combining Pd(II) and Ln(III) with 2,2 -bipyridine-4,4 -dicarboxylic acid (H2BPDC) as a heteroleptic
ligand, under hydrothermal conditions, and structurally characterized by means of single-crystal X-ray
diffraction, FT-IR, powder X-ray diffraction, elemental analysis and thermogravimetric (TG) techniques.
Single-crystal X-ray diffraction examination showed that 1–3 have similar 3D frameworks, connected
via hydrogen bonding interactions, and consisting of three distinct types of building blocks: Pd(BPDC)Cl2,
Pd(HBPDC)2 and a Ln dimer (Ln2O15). The new isostructural, air and water stable coordination polymers,
resulting from association of lanthanides with palladium, exhibited superior but distinct capabilities as
eco-friendly heterogeneous catalysts in Suzuki-Miyaura, Heck and Sonogashira cross-couplings, under
green reaction conditions. Supramolecular, solid catalysts 1–3 have been recovered quantitatively
from the reaction mixtures by simple filtration. Also importantly, their sustainability, utility and
cost-effectiveness have been demonstrated by recycling experiments with catalyst 1 in Suzuki-Miyaura,
proceeding practically without loss of activity after four runs.
1
0 November 2015
Accepted 24 November 2015
Available online 28 November 2015
Keywords:
Heterobimetallic coordination polymers
Catalysis
Heterogeneous catalysts
Recyclable catalyst
Green carbon–carbon coupling reactions
©
2015 Elsevier B.V. All rights reserved.
1
. Introduction
broad range of transition and non-transition metals associated with
various organic ligands have been thoroughly screened to obtain
novel hybrid materials endowed with desired physical-chemical
characteristics, e.g. crystal size and shape, inner porosity, surface
area, catalytic activity, mechanical, optical, electrical and magnetic
properties or chemical reactivity [9]. In some instances, an inge-
nious valorization of the assets of transition metals and lanthanides
in functional organic-inorganic networks proved to be a convenient
strategy for engineering the new materials designed for advanced
applications [10].
A major utilization of porous coordination polymers regards
the efficient heterogeneous catalysis of diverse chemical transfor-
mations leading to useful reaction products [11]. In addition to
profitably modelling the catalyst activity and selectivity in these
processes, this class of solid catalysts affords easy handling, facile
separation and purification of products, good stability and recy-
clability while also working under mild conditions [12]. These
attributes have not only great economical outcome but also key
The high interest in the rapid development of novel composite
nanomaterials based on emerging generations of porous coordi-
nation polymers (PCPs) [1–3] is due to their valuable properties,
suitable for appealing applications in many technologically impor-
tant fields [4–6]. Such hybrid frameworks possess the unique
feature that their crystalline structure, composition and function-
ality can be finely tuned by a proper variation of the inner metal
clusters and adequate selection of the flexible organic ligands [7]
as well as by advanced post-synthetic modification and function-
alization [8]. By using a clever linker design and ‘metalloligand’
methodology to incorporate specific functional metallic sites, a
∗ Corresponding authors. Fax: +86 24 89389359.
E-mail addresses: vdragutan@yahoo.com (V. Dragutan),
sunyaguang@yahoo.com (Y. Sun).
http://dx.doi.org/10.1016/j.apcata.2015.11.044
0
926-860X/© 2015 Elsevier B.V. All rights reserved.

2
L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
significance in the rapid development of environmentally benign
chemical processes [12e]. Of particular interest is their efficient
application for constructing complex, bio-active organic molecules
by versatile cross carbon–carbon couplings like Suzuki-Miyaura,
Heck, Negishi and Sonogashira reactions [10a,13,14].
display a reasonably robust and stable structural pattern with
enhanced physical and chemical features, dependent on the nature
of the lanthanide incorporated. Such novel, porous heterobimetal-
lic coordination polymers, endowed with unprecedented physical
traits and versatile chemical reactivity and chemoselectivity, will
allow access to quite active, water tolerant, easily separable and
recyclable solid catalysts, suitable for superior applications in eco-
friendly and cost-effective Suzuki-Miyaura, Heck and Sonogashira
reactions.
Palladium-catalyzed cross-couplings rank among most popular
reactions for production of fine chemicals at ton-scale, especially
in the pharmaceutical industry. As established powerful tools for
creating C C bonds, they have been widely investigated in both
homogeneous and heterogeneous phase for the synthesis of a host
of organic compounds [13,14]. A large platform of palladium cat-
alysts bearing a diversity of ancillary ligands (phosphine, arene,
bipyridine, pincer, N-heterocyclic carbene (NHC), acyclic diamino
carbene (ADC), etc.) has been created and successfully applied for
many synthetic purposes [15]. Nonetheless, certain cross-coupling
reactions promoted by today palladium catalysts in homogeneous
phase use uncommon, expensive ligands or occasionally suffer
from significant waste of the costly palladium catalyst which can
not be recovered and recycled [15]. On the other hand, although
immobilization of homogeneous palladium complexes on solid
supports facilitates catalyst separation, allows cross-coupling reac-
tions in water and improves leaching resistance and recycling,
some supported catalysts involve important disadvantages such
as, tedious and expensive preparation of the immobilized cata-
lyst, additional steric restraints imposed to the substrates, uneven
distribution of the active sites, uncontrolled catalyst loading, all
of which in many cases raise difficulties in developing large scale
applications [16].
2. Experimental
2.1. Materials and physical–chemical measurements
All chemicals were purchased commercially and used without
further purification. All syntheses were carried out in 23 mL Teflon-
lined autoclaves under autogenous pressure. The reaction vessels
were filled to approximately 50% volume capacity. Water used in
the synthesis was distilled before use. The C, H and N elemental
analysis was performed on a PerkinElmer 240C elemental analyzer.
FT-IR spectra using KBr pellets were recorded using a Nicolet IR-470
spectrometer. TG analysis was carried out on a SDT Q600 instru-
◦
−1
ment with a heating rate of 10 C min . Powder X-ray diffraction
(PXRD) patterns of the samples were collected on an X-ray diffrac-
tometer (BRUKER D8 ADVANCE) with Cu K␣ radiation. GC analyses
were performed on an Agilent Technologies 7890A gas chromato-
1
graph fitted with an HP-5 column (30 m × 320 ␮m × 0.25 ␮m).
H
NMR spectra were recorded on a Bruker BioSpin GmbH AVANCE III
500 MHz spectrometer operating at 500 MHz. The amount of pal-
ladium was determined by Shimadzu AA-6300C atomic absorption
spectrophotometer.
To overcome the above problematic issues, efforts have been
recently devoted to create new functional hybrid materials by
thoroughly tailoring the organic ligands coordinated at palladium
[
7,17] or by substituting purely organic linkers with designed
metalloligands endowed with highly active and chemoselective
sites. Further progress has been made in their functionalization by
appropriate post-synthetic methods [8] and in elaborating inno-
vative flow techniques [18a,b], microwave-assisted procedures
2.2. Synthesis of catalysts 1–3
2.2.1. Synthesis of
[Pr Pd (BPDC) (HBPDC) (ꢀ -O)Cl (H O) ·5H O]m (1)
2
3
2
2
2
4
2
6
2
[
[
18c,d] as well as palladium nanoparticle or supported catalysts
19]. Combination of Pd with other metals to ensure synergis-
Synthesis of 1–3 proceeded under hydrothermal conditions cur-
rently applied in our group in both the Pd [20] and lanthanide
tic interactions has been a promising option [10a,b]. However,
examples of Pd-Ln systems are surprisingly scarce [10]. In their
work on Suzuki-Miyaura and Heck reactions between substi-
tuted aryl halides and phenylboronic acid or olefins, in presence
series [1c,d]. For 1, a mixture containing K PdCl4 (0.145 mmol),
2
Pr(NO ) ·6H O (0.09 mmol), H BPDC (0.145 mmol), water (7 mL)
3
3
2
2
−
1
and 0.01 mol L NaOH (4 mL) was sealed in a Teflon-lined stain-
less steel vessel (23 mL) which was heated at 90 C for 96 h and
◦
ꢀ
of heterobimetallic Pd-Ln systems (Ln = Sm, Eu, Gd, Tb; 2,2 -
then cooled to room temperature in 48 h. Yellow rhombic crystals
of 1 were obtained and picked out, washed with distilled water and
dried in air (Yield: 44.6% based on Pr). Elemental analysis Calcd (%)
for C48H48Cl N O Pd Pr : C 29.83; H 2.39; N 5.67. Found: C 29.91;
ꢀ
bipyridine-5,5 -dicarboxylic acid as organic linker), Jin et al. [10a]
using specific conditions (0.5 mol% catalyst loading and tempera-
◦
tures of 90 and 100 C) have successfully improved the reaction
4
8
28
3
2
−
1
performance with respect to the catalyst activity. Whereas a high
activity of the Pd-Ln initiator was recorded and the catalyst leaching
was at a minimum, data on catalyst stability, recovery and recy-
cling are still to be unveiled. Moreover, in spite of these remarkable
advancements in palladium C C cross-coupling catalysis, impor-
tant environmental aspects related to the physical profile of the
heterogeneous catalysts, chemical activity and stability, leaching
or recovery and recycling are still of concern. With the aim of
widening the scope and application area of coordination poly-
mers in environmentally friendly catalytic C C cross-coupling
processes, here we report the facile construction of a new set
of robust, air- and water-stable heterobimetallic coordination
polymers i. e. [Ln Pd (BPDC) (HBPDC) (ꢀ -O)Cl (H O) ·nH O]m
H 2.51; N 5.81. IR (KBr, cm ): 3416s, 1625s, 1552s, 1385vs, 1291w,
1237w, 780m, 699m.
2.2.2. Synthesis of
[Gd Pd (BPDC) (HBPDC) (ꢀ -O)Cl (H O) ·4H O]m (2)
2
3
2
2
2
4
2
6
2
A mixture containing K PdCl (0.145 mmol), Gd(NO ) ·5H O
2
4
3
3
2
−
1
(0.09 mmol), H BPDC (0.145 mmol), water (6 mL) and 0.01 mol L
2
NaOH (6 mL) was sealed in a Teflon-lined stainless steel vessel
◦
(23 mL) which was heated at 70 C for 96 h and then cooled to
room temperature in 48 h. Yellow rhombic crystals of 2 were
obtained and collected, washed with distilled water and dried in
air (Yield: 48.3% based on Gd). Elemental analysis Calcd (%) for
C48H46Cl N O Pd Gd : C 29.37; H 2.20; N 5.59. Found: C 29.68; H
2
3
2
2
2
4
2
6
2
4
8
27
3
2
−
1
(
Ln = Pr, n = 5(1); Ln = Gd, n = 4(2); Ln = Tb, n = 4(3)), by a reticular
2.39; N 5.77. IR (KBr, cm ): 3422s, 1626s, 1552m, 1384vs, 1291w,
1245w, 778m, 670m.
synthesis approach, combining for the first time the nitrophilic Pd
ꢀ
units and oxophilic Ln motifs through the heteroleptic ligand, 2,2 -
ꢀ
bipyridine-4,4 -dicarboxylic acid, as suitable, bifunctional organic
2.2.3. Synthesis of
linker. It is anticipated that, by properly engineering the Pd net-
work through inclusion of lanthanides by intermediacy of a totally
different organic vector, the newly created hybrid materials will
[Tb Pd (BPDC) (HBPDC) (ꢀ -O)Cl (H O) ·4H O]m (3)
2
3
2
2
2
4
2
6
2
A mixture containing K PdCl (0.145mmol), Tb(NO ) ·6H O
2
4
3
3
2
−
1
(0.09 mmol), H BPDC (0.145 mmol), water (6 mL) and 0.01 mol L
2

L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
3
NaOH (6 mL) was sealed in a Teflon-lined stainless steel vessel
uct was isolated by column chromatography. All reaction products
were identified by GC–MS and 1H NMR spectra.
◦
(
23 mL) which was heated at 70 C for 96 h and then cooled to
room temperature in 48 h. Yellow rhombic crystals of 3 were
obtained and collected, washed with distilled water and dried in
air (Yield: 42.5% based on Tb). Elemental analysis Calcd (%) for
C48H46Cl N O Pd Tb : C 29.34; H 2.15; N 5.95. Found: C 29.63; H
2
.4.3. General experimental procedure for the Sonogashira
reaction
mixture of aryl halide (1.0 mmol), phenylacetylene
4
8
27
3
2
A
−1
2
.38; N 5.76. IR (KBr, cm ): 3418vs, 1623s, 1537m, 1374m, 1282w,
236m, 764s, 688m.
ꢀ ꢀ
1.5 mmol), K CO3 (1.5 mmol), 2,2 -bipyridine-4,4 -dicarboxylic
2
(
1
acid (0.005 mmol), CuI (0.012 mmol), DMF-H O (1:1, 6 mL), Bu NCl
2
4
◦
1.0 mmol) and 0.4 mol% of catalyst was stirred at 100 C in argon.
(
Progress of the reaction was monitored by GC–MS. Yields, calcu-
lated from GC, were based on the amount of aryl halide employed.
At the end of the reaction, the mixture was poured into a saturated
NaCl aqueous solution (10 mL) and extracted with ethyl acetate
2
.3. X-ray crystallography
The collection of single-crystal crystallographic data was carried
out on a Bruker SMART Apex CCD diffractometer using graphite-
monochromated Mo K␣ radiation (0.71073 Å) at 293 K in the ω-2Â
scan mode. An empirical absorption correction was applied to the
data using the SADABS program [21]. The structures were solved
(20 mL). The organic phases were combined, and the volatile
components were evaporated in a rotary evaporator. The crude
product was purified by column chromatography on silica gel. All
reaction products were identified by GC–MS and 1H NMR spectra.
by direct methods and refined by full-matrix least squares on
2
F
using the SHELXTL crystallographic software package [22]. All
non-hydrogen atoms were refined anisotropically. Hydrogens were
placed in calculated positions and refined using a riding mode.
From the perspective of charge balance, both carboxyl groups
should be deprotonated in one ligand and only one carboxyl group
should be deprotonated in the other ligand of the asymmetric
unit of compounds 1–3. After carefully measuring all C-O bond
lengths, we found that certain bond lengths (C12-O3A = 1.332 Å,
C12-O3B = 1.307 Å in 1, C12-O3 = 1.276 Å in 2, and C24-O7 = 1.291 Å
in 3) in the respective carboxyl groups are far larger than those of
the other C O bonds without any distance restrained commands,
indicating that the former carboxyl groups were not deprotonated.
Therefore, the hydrogen atoms were added on these oxygen atoms
except in 1 (O3 is disorder). The data completeness of 92.8% is a lit-
tle low in the crystal data of 3 (as mentioned in alert A), but it cannot
affect the structure confirmation. CCDC: 1020991(1); 1020990(2);
2.4.4. Hot-filtration test and catalyst recycling
The hot filtration test for the Suzuki-Miyaura reaction was
carried out according to the standard procedure. After 0.5 h the
reaction mixture was filtered at the reaction temperature to remove
the solid catalyst, then the mother liquor was allowed to react
for another 9 h under identical conditions and the conversion was
monitored by GC at different time intervals (see Section 3.3.4).
To quantitatively determine the amount of palladium in the final
reaction solution atomic absorption spectrophotometry (AAS) was
used; no traces of palladium could be detected in the filtrates from
the reaction mixtures.
Reusability of the catalyst 1 was studied in the Suzuki-Miyaura
cross-coupling reaction of 4-bromoacetophenone and phenyl-
boronic acid. After completion of the reaction, the catalyst was
recovered by simple filtration and washed with ethyl acetate, fol-
lowed by an important amount of water to remove the base, then
was dried under vacuum. The recovered catalyst was employed
in the next run, with a new addition of substrates in appropriate
amount, under the established optimum reaction conditions (see
Section 3.3.4). After the catalytic reaction, the crystalline state of
catalyst 1 was analyzed by powder X-ray diffraction.
1
020989(3).
2.4. Catalytic reactions
2.4.1. General experimental procedure for the Suzuki coupling
reaction
A mixture of aryl halide (1.0 mmol), arylboronic acid (1.2 mmol),
K CO (2.0 mmol), DMF-H O (1:1, 6 mL), and 0.4 mol% of catalyst
3. Results and discussion
2
3
2
◦
was stirred at 70 C in air for 3 h. Progress of the reaction was mon-
itored by withdrawing samples periodically that were analyzed
by GC–MS. Yields, calculated from GC, were based on the amount
of aryl halide employed. At the end of the reaction, the catalyst
was separated by simple filtration. The mixture was extracted with
diethyl ether (20 mL), washed with water and dried over anhydrous
3.1. Crystallographic structure and characterization of
compounds 1–3
Crystal and structural refinement data for 1–3 are displayed
in Table 1 while important bond lengths and angles are listed in
Table S1. Compounds 1–3 are isomorphous, and crystallize in the
monoclinic space group P2/c. Therefore, only the structure of 1
will be described in detail. The coordination environments around
the Pd and Pr metal centers are illustrated in Fig. 1. The crystal
structure of 1 contains two crystallographically independent Pd
atoms. Pd1 constructs a square planar coordination mode con-
Na SO . The solvent was completely removed from the extract
2
4
with a rotary evaporator to obtain the product, which was further
purified by column chromatography on silica gel. All reaction prod-
ucts were identified by gas chromatography-mass spectroscopy
1
(
GC–MS) and H NMR spectra.
necting two nitrogen atoms in a BPDC2 ligand and two chlorine
atoms in the remaining cis-positions with the average bond dis-
tances of d(Pd − N) = 2.02 Å and d(Pd − Cl) = 2.28 Å, respectively. The
−
2.4.2. General experimental procedure for the Heck reaction
A mixture of aryl halide (1.0 mmol), styrene (1.5 mmol), K CO3
2
◦
(
2.0 mmol), DMF-H O (1:1, 6 mL), and 0.4 mol% of catalyst was
N − Pd − N angle in 1 decreases from the normal 90 to around
2
◦
◦
heated to 90 C in air for 10 h. Progress of the reaction was mon-
itored by periodically withdrawing samples from the reaction
mixture and analyzing them by GC–MS. Yields, calculated from GC,
were based on the amount of aryl halide employed. The resulting
reaction mixture was filtered and washed with a saturated NaCl
aqueous solution (10 mL) and extracted with ethyl acetate (20 mL).
The organic phase was separated and dried over Na SO , and ethyl
81.0 . Correspondingly, the Cl − Pd − N angle expands from the
◦
◦
normal 90 to an average of 94.8 , indicating a typical mode of
cis-chelating bipyridine. Pd2 has a similar coordination mode to
Pd1, being coordinated by the four nitrogen atoms of two HBPDC
−
1
ligands. Two crystallographically equivalent Pr atoms in 1 form Pr
dimers with d(Pr − Pr) = 4.48 Å. Each Pr atom coordinates with eight
oxygen atoms, a ꢀ -O atom bridges the two Pr atoms of the dimer,
2
4
2
acetate was evaporated under reduced pressure. The final prod-
four are carboxylate oxygen atoms from different H BPDC ligands
2

4
L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
Table 1
Crystal data and structure refinement for 1–3.
1
2
3
Formula
C48H48Cl4N8O28Pd3Pr2
C48H46Cl4N8O27Pd3Gd2
C48H46Cl4N8O27Pd3Tb2
Fw
1927.76
293(2)
Monoclinic
P2/c
17.756(4)
7.052(14)
25.693(5)
106.15(3)
3090.2(11)
2
1942.43
293(2)
Monoclinic
P2/c
17.560(3)
6.973(14)
25.330(5)
106.34(3)
2976.3(10)
2
1945.77
293(2)
Monoclinic
P2/c
17.683(3)
6.991(14)
25.531(5)
106.12(3)
3032.2(10)
2
Temp (K)
Cryst system
Space group
a (Å)
b (Å)
c (Å)
◦
␤
( )
3
V (Å)
Z
ꢁ
calc (g cm−3)
2.072
2.669
2.167
3.360
2.131
3.443
−
1
ꢀ/mm
F(000)
1880
1880
1884
Reflns collected/unique
GOF
30211/7118
1.108
0.0515
18041/5141
1.050
0.0816
18690/4965
1.010
0.0589
a
R1 (I > 2ꢂ(I))
wR2b
0.1214
0.1953
0.1273
a
R1 = ꢃ||Fo| − |Fc||/ꢃ|Fo|.
b
wR2 = {ꢃ[w(Fo − Fc )2]/ꢃ[w(Fo2) ]}1/2.
2
2
2
Fig. 1. View of the coordination environments of the Pr(III) and Pd(II) ions in catalyst 1. The free H2O molecules and hydrogen atoms were omitted for clarity. Symmetry
codes: (a) -x, y, 1.5 − z; (b) 1 − x, y, 1.5 − z; (c) x, 1 − y, 0.5 + z; (d) −x, 1 − y, 1 − z.
◦
◦
with d(Pr − O) around 2.36–2.50 Å, while the remaining three oxy-
gen atoms are terminal water molecules with the d(Pr − O) around
ring from 120 C to 370 C is about 10.17%, corresponding to the
loss of the coordinated and free water molecules (calcd: 10.28%).
◦
2
.43–2.53 Å.
The catalyst is stable up to 370 C and decomposes above this tem-
It is worth pointing out that the crystal structure of 1 is built up of
perature. The thermogravimetric study thus shows that the Pd(II)
compounds degrade at considerably high temperatures.
Powder X-ray diffraction (PXRD) analysis of compounds 1–3 was
performed at room temperature (Fig. S3). The patterns for 1–3 are in
good agreement with the calculated ones obtained from the single-
crystal structures, indicating that the single-crystal structure is
really representative for the main constituent of the corresponding
sample.
three distinct types of building blocks: Pd(BPDC)Cl , Pd(HBPDC) ,
2
2
and the Pr dimer (Pr O15). The Pr dimers are connected alterna-
2
tively by the building blocks of Pd(BPDC)Cl2 to form a 1D linear
chain along the c axis (Fig. 2). The building blocks of Pd(HBPDC)2
further connect the Pr dimers into infinite 1D chains to construct a
D layer in the ac plane (Fig. 3). Moreover, the 2D layers are assem-
bled into a 3D framework via hydrogen bonding interactions (Fig.
S1).
2
3
3
.3. Catalytic activities
3.2. TG analysis and PXRD
.3.1. Suzuki-Miyaura cross-coupling reaction
Thermogravimetric (TG) analysis was performed, in a nitrogen
The performance of the Suzuki reaction is dependent on a vari-
atmosphere, on polycrystalline samples of compounds 1–3, and the
TG curves are shown in Fig. S2. As the curves of the three com-
pounds are similar, only that of catalyst 1 will be discussed in detail
as a representative compound. The first weight loss of 1 occur-
ety of parameters such as the substrate nature, the catalyst type and
its structure, the solvent, base, and temperature. To explore the cat-
alytic activity of our new heterobimetallic catalysts, we based our
investigation on the standard Suzuki-Miyaura cross-coupling reac-

L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
5
Fig. 2. One-dimensional chain of catalyst 1.
Fig. 3. Two-dimensional layer (left) and topology (right) of catalyst 1.
Table 2
Optimization of reaction conditions for the Suzuki-Miyaura coupling of 4-bromoacetophenone with phenylboronic acid, catalyzed by 1.
a
◦
Yield(%)b
Entry
Solvent
Base
T/ C
Time/h
1
2
3
4
5
6
7
8
9
Toluene
H2O
DMF
K2CO3
K2CO3
K2CO3
K2CO3
t-C4H9ONa
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
None
100
90
100
70
70
50
25
70
90
70
70
12
12
12
3
3
7
7
1.5
3
12
12
31
59
5
DMF-H2O
DMF-H2O
DMF-H2O
DMF-H2O
DMF-H2O
DMF-H2O
DMF-H2O
DMF-H2O
91
71
87
72
83
88
c
1
0
1
0
1
0
a
b
c
Reaction conditions: 4-bromoacetophenone (1.0 mmol), phenylboronic acid (1.2 mmol), catalyst (0.4 mol%).
Yields were determined by GC and GC–MS analyses.
No catalyst.
tion of 4-bromoacetophenone and phenylboronic acid starting with
catalyst 1. The reaction conditions were systematically optimized,
and the results are presented in Table 2. A control experiment indi-
cated that, as expected, the coupling reaction did not occur in the
absence of catalyst (entry 10). It was found that, among the tested
solvents, unsatisfactory yields were obtained with single solvents
improve significantly (Table 2, entries 4–9). The organic/aqueous
co-solvent is conducive to solve the solubility problems of the
organic reactants and the inorganic base thus accelerating the reac-
tion. Moreover, it appears that water, in addition to better solving
the inorganic base, has a beneficial kinetic effect on the trans-
metallation step of the catalytic cycle enhancing solvation of the
inorganic and boronic salts involved in Suzuki-Miyaura reaction.
This effect may not occur in conventional organic solvents like
◦
like toluene, DMF or water, even at 100 C and increased reaction
times (Table 2, entries 1–3). However, a 1:1 mixture of DMF-H O
2
proved an efficient system for the cross-coupling making yields to
toluene [10a]. After selecting DMF-H O (v/v = 1:1) as the optimal
2

6
L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
solvent combination, bases have been in turn screened. The base
has previously been demonstrated to play a significant role in
Suzuki-Miyaura cross-coupling reactions [23]. As shown in entry
1
1, Table 2, the reaction cannot be carried out in the absence of base.
It became clear from the results that the inorganic base, K CO , was
2
3
much more suitable than the organic one (Table 2, entry 4 vs. 5).
Also, the temperature and time are essential reaction parameters
(Table 2, entries 6 vs. 7 and entry 4 vs. 8). At room temperature, the
yield dropped to 72% (Table 2, entry 7). We found that using K CO
2
3
◦
as the base, in DMF-H O (1:1) at 70 C and 3hr reaction time, gave
2
the coupled product in the best yield.
Having established the optimal reaction conditions, we then
investigated the reaction using various aryl halides bearing
electron-donating and electron-withdrawing groups in the para
position which were coupled with arylboronic acids. As shown in
Table 3, catalysts 1–3 displayed approximately the same catalytic
activities leading to similar yields. Therefore, catalyst 1 was cho-
sen as a model and further applied in other types of cross-coupling
reactions. It is commonly believed that higher yields are achieved
for aryl halides endowed with electron-withdrawing rather than
electron-donating substituents. In our case this could be evidenced
by the parallel reactions of aryl iodides bearing electron-releasing
or electron-accepting substituents and phenylboronic acid (Table 3,
entries 6–8). Substituted arylboronic acids were also tested to fur-
nish the corresponding biaryl products (Table 3, entries 9–13). In
contrast to the effects of substituents on the aryl halides, a bet-
ter activity with the catalyst 1 containing Pr was observed for
electron-rich relative to electron-poor arylboronic acids (Table 3,
entry 10 vs. 13). As expected, aryl chlorides were less reactive than
aryl bromides and iodides. A rationale for these outcomes is the
much higher C Cl bond strength (vs. C Br and C I) [24] account-
ing for the lower yields obtained (Table 3, entries 14–15). It is
worth mentioning that the obtained yields for the catalyst load-
ings and eco-friendly reaction conditions used in our studies are
in good agreement with previous reports [10a] on Suzuki-Miyaura
cross-coupling with Pd-Ln systems where similar substrates but
toluene as a solvent, higher temperatures and slightly longer times
have been employed. Only in special cases (for highly hindered
substrates or much elaborated, expensive Pd catalysts [13a]) the
reported performance can significantly differ from ours.
Fig. 4. Plots of conversion versus time for the Suzuki-Miyaura cross-coupling reac-
tion of 4-bromoacetophenone with phenylboronic acid in the presence of 1 (solid
line). Also shown is the conversion of the same reaction upon removal of 1 by
filtration after only 0.5 h reaction time (dashed line).
3.3.3. Sonogashira cross-coupling reaction
The encouraging results from the Suzuki and Heck reactions, led
us to also examine the catalytic behaviour of 1–3 in the Sonogashira
cross-coupling. To our delight, 1–3 were active enough to promote
the Sonogashira reactions of various aryl halides and phenyl acety-
lene in good yields (Table 5). It was found that the reaction run in
DMF-H2O using K2CO3 as the base, a small amount of H2BPDC, CuI
as co-catalyst and tetrabutylammonium chloride (TBAC) as phase
◦
transfer agent, at 100 C under argon, displayed the best perfor-
mance. Comparison of entries 1 and 4, entries 5 and 6, or entries
7 and 8 evidences that the yield improved slightly, not sharply,
when CuI was added, what suggests that the activity of the cat-
alyst itself is high. That, however, CuI plays a role in facilitating
the transmetallation step of the catalytic cycle [26] is clearly evi-
denced in this work by the drop in yield in its absence (Table 5, entry
7). Aryl halides bearing electron-withdrawing or electron-donating
groups showed obvious differences in reactivity with phenyl acety-
lene (entries 1, 6 and 8 in Table 5), indicating that under the tested
conditions the reaction is sensitive to electronic effects of the sub-
stituents. As expected, aryl bromides and aryl chlorides were less
reactive than aryl iodides (entries 9–12 in Table 5).
3.3.2. Heck cross-coupling reaction
Stimulated by the above results obtained with catalysts 1–3
in the Suzuki-Miyaura reaction, our attention next turned to the
palladium-catalyzed Heck cross-coupling reaction of aryl halides
with styrene, an extremely valuable method for carbon carbon
bond formation. In activity studies with our catalysts in the Heck
contextHeckhh, an excess of styrene with respect to the aryl halide
3
.3.4. Heterogeneity test and recyclability
A hot-filtration test was carried out in the Suzuki-Miyaura cross-
coupling reaction of 4-bromoacetophenone with phenylboronic
acid to determine whether the reaction proceeds in a heteroge-
neous or a homogeneous phase. When catalyst 1 was removed
by filtration after only half an hour, just a 40% conversion was
recorded. Upon additional standing for 9.5 h of the filtrate, we found
that no further conversion has taken place (Fig. 4), indicating the
absence of catalyst in the filtrate. The important conclusions here
are twofold: that a perfect separation and recovery of the solid cat-
alyst can be achieved and plus that the catalytic system can be
reused.
Recovery and reuse of the catalyst are important issues in
environmentally benign coupling reactions [12d]. Easy catalyst
separation and recycling in successive batch operations can greatly
increase the economic outcome of the reaction. Tests were run on
catalyst 1 in the Suzuki-Miyaura cross-coupling as a model reac-
tion. In four consecutive runs high yields have been attained (over
(
molar ratio = 1.5) was customarily employed to avoid the forma-
tion of homocoupling by-products. A series of experiments, run to
optimize the reaction parameters, indicated that best results can be
attained with tetrabutylammonium chloride (TBAC) as phase trans-
fer agent, K CO as the base, in DMF-H O as the solvent (Table 4).
2
3
2
The coupling reactions of aryl iodides and substituted aryl bro-
mides with styrene proceeded smoothly and all products showed
E configuration. Moreover, substituents on the aromatic ring of the
aryl halides had a significant effect on the yields, para-substituted
aryl iodides with electron-withdrawing groups reacting faster than
those with electron-donating groups (Table 4, entries 1 and 4), yet
aryl chlorides gave no conversion (entries 8–9). Compared with
substituted aryl bromides, the reaction of bromobenzene led to a
much lower product yield (entries 6 vs. 7). Again the role of water
as cosolvent was similar to that observed in many “solid–liquid”
phase-transfer catalyzed organic processes in which the impor-
tance of water has been well evidenced [25].
8
5% yield in the fourth cycle, hence a loss of just 7% of the initial
catalytic activity) (Fig. 5). Noteworthy also, the catalyst structure is
preserved throughout the catalytic process. PXRD analysis shows

L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
7
Table 3
Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids using Pd − Ln catalysts 1–3.
a
Entry
R1
R2
X
Catalystb
Yield(%)c
1
2
3
4
5
6
7
8
9
CH3CO
CH3CO
CH3CO
NO2
H
H
CH3
CH3CO
H
CH3CO
NO2
H
H
H
H
H
H
H
H
H
Br
Br
Br
Br
Br
I
1
2
3
1
1
1
1
1
1
1
1
1
1
1
1
91
89
92
89
86
80
90
93
91
92
94
89
70
Trace
22
I
I
CH3
CH3
CH3
CH3CO
CH3CO
H
Br
Br
Br
Br
Br
Cl
Cl
1
1
1
1
1
1
0
1
2
3
4
5
CH3CO
CH3
CH3CO
H
a
b
c
Reaction conditions: aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2.0 mmol), DMF-H2O (1:1, 6.0 mL), catalyst (0.4 mol%), 3 h.
[Pd − Pr], 2 [Pd − Gd], 3 [Pd − Tb].
Yields were determined by GC and GC–MS analyses.
1
Table 4
a
Heck cross-coupling reaction of aryl halides and styrene using Pd − Ln catalysts.
Entry
R
X
Catalystb
Yield(%)c
1
2
3
4
5
6
7
8
9
CH3CO
CH3CO
CH3CO
CH3
H
H
CH3CO
CH3
CH3CO
I
I
I
I
1
2
3
1
1
1
1
1
1
83
83
85
77
80
23
63
0
I
Br
Br
Cl
Cl
0
a
Reaction conditions: aryl halide (1.0 mmol), styrene (1.5 mmol), K2CO3 (2.0 mmol), DMF-H2O (1:1, 6.0 mL), TBAC (1.5 mmol), catalyst (0.4 mol%), 10 h.
b
c
1
[Pd − Pr], 2 [Pd − Gd], 3 [Pd − Tb].
Yields were determined by GC and GC–MS analysis.
Table 5
a
Sonogashira cross-coupling reaction of aryl halides and phenylacetylene using Pd − Ln catalysts.
Entry
R
X
Catalystb
Yield(%)c
1
2
3
4
5
6
7
8
9
CH3CO
CH3CO
CH3CO
CH3CO
CH3
CH3
H
H
H
I
I
I
I
I
I
I
I
Br
Br
Cl
Cl
1
2
3
1
1
1
1
1
1
1
1
1
80
79
83
d
76
60
d
77
51
d
64
trace
12
trace
trace
1
1
1
0
1
2
CH3CO
CH3
CH3CO
a
Reaction conditions: aryl halide (1.0 mmol), phenylacetylene (1.5 mmol), K2CO3 (1.5 mmol), DMF-H2O (1:1, 6.0 mL), catalyst (0.4 mol%), H2BPDC (0.005 mmol), TBAC
(
1 mmol), CuI (0.012 mmol), 8 h.
b
1
[Pd − Pr], 2 [Pd − Gd], 3 [Pd − Tb].
c
Yields were determined by GC and GC–MS analyses.
No CuI.
d

8
L. You et al. / Applied Catalysis A: General 511 (2016) 1–10
Liaoning province (No. 2013204). F.D. acknowledges the Educa-
tional Bureau of Liaoning Province for Fundamental Research of
Key Lab (No. LZ2014028). I.D. and V.D. gratefully acknowledge sup-
port from the Romanian Academy, Institute of Organic Chemistry
“C.D. Nenitescu”, Bucharest. Special thanks are due to the Review-
ers and the Editor for their kind and helpful suggestions regarding
the manuscript.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.apcata.2015.11.
0
44.
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