Novel functionalized microporous organic networks based on triphenylphosphine

Article abstract of DOI:10.1002/chem.201300334

This article describes the synthesis and functions of phosphine or phosphine oxide functionalized networks (PP-P or PP-PO; PP=porous polymer). These materials were predominantly microporous and exhibited high surface areas (S_BET: 1284 and 1353 m² g^-1 for PP-P and PP-PO, respectively), with high CO₂ (2.46 and 3.83 mmol g^-1 for PP-P and PP-PO, respectively) uptake capacities. Pd nanoparticles can be simply incorporated into the functionalized networks (PP-P-Pd or PP-PO-Pd) through a facile one-step impregnation. A yield of 98 % was obtained in the Suzuki reaction between 1-chlorobenzene and p-tolylboronic acid with the PP-P-Pd system, which was higher than that obtained when PP-PO-Pd (53.2 %) or [Pd(PPh₃)₄] (38.2 %) was used as the catalyst. The superior catalytic ability of PP-P-Pd can be attributed to the structural features that incorporate triarylphosphine within a microporous structure. Phosphine sponges: Microporous polymers (see figure) with phosphine or phosphine oxide as connecting nodes were prepared. These materials exhibit high surface areas and excellent carbon dioxide capture capacities. Pd nanoparticles supported on the polymeric networks were also prepared; they exhibit high catalytic activity for Suzuki reactions. Copyright

Full text of DOI:10.1002/chem.201300334

DOI: 10.1002/chem.201300334
Novel Functionalized Microporous Organic Networks
Based on Triphenylphosphine
Qiang Zhang,[a, b] Yanqin Yang,[a, b] and Suobo Zhang*[a]
À À
Abstract: This article describes the syn-
thesis and functions of phosphine or
phosphine oxide functionalized net-
nanoparticles can be simply incorporat-
ed into the functionalized networks
tolylboronic acid with the PP P Pd
system, which was higher than that ob-
À À
À
À
À
À
(PP P Pd or PP PO Pd) through a
facile one-step impregnation. A yield
of 98% was obtained in the Suzuki re-
action between 1-chlorobenzene and p-
tained when PP PO Pd (53.2%) or
[Pd(PPh3)4] (38.2%) was used as the
catalyst. The superior catalytic ability
of PP P Pd can be attributed to the
structural features that incorporate tri-
À
À
works (PP P or PP PO; PP=porous
polymer). These materials were pre-
dominantly microporous and exhibited
ACHTUNGTRENNUNG
À À
high surface areas (SBET
:
1284 and
À
1353 m2 gÀ1 for PP P and PP PO, re-
spectively), with high CO2 (2.46 and
arylphosphine within
structure.
a microporous
À
Keywords: carbon storage · hetero-
geneous catalysis · microporous ma-
terials · nanoparticles · phosphines
3.83 mmolgÀ1 for PP P and PP PO,
respectively) uptake capacities. Pd
À
À
Introduction
state.[7] Among other features, microporous polymer net-
works possess robustness and scalability, the materials have
good thermal and excellent chemical stability (e.g., in the
presence of strong acids and bases), and can be readily pro-
duced on a large scale. Such materials have been used as
sorbents for organic vapors,[7] for the recovery of organic
compounds from water,[8] and in heterogeneous catalytic sys-
tems.[9]
Most of the microporous polymer networks synthesized to
date have been produced as intractable solids and their
chemical functionalization was therefore limited.[6,10] The de-
velopment of porous materials containing functional groups
to fulfill a certain task is a pertinent requirement.[7–9] Func-
tionalization of microporous polymers could open up
second-generation porous materials with useful combined
chemical and physical properties.[1c,4b,11] Recently, many mi-
croporous organic polymers containing functional units such
as bipyridine, metalloporphyrin, and triazine rings, have
been reported.[12] These materials exhibit excellent proper-
ties such as superior catalytic activity and high CO2 uptake
capacity.[12]
The synthesis and application of microporous organic poly-
mers (MOPs) has recently spurred scientific interest within
the fast developing field of material science.[1] Their most
prominent feature of high intrinsic levels of porosity along
with diverse and simple chemical routes available for their
synthesis makes these materials attractive candidates for a
variety of applications in areas such as molecular separa-
tions, heterogeneous catalysis, and gas storage.[1] MOPs can
be distinguished, according to recent reports, into 1) micro-
porous polymer networks, such as the well-described hyper-
cross-linked resins,[2] 2) a class of porous covalent organic
framework,[3] 3) conjugated microporous polymers,[4] and 4)
polymers with intrinsic microporosity (PIMs).[5] Microporous
polymer networks represent a family of robust porous or-
ganic polymer networks with high BET surface areas that
can exceed 1000 m2 gÀ1.[6] Unlike solution-processable PIMs,
the permanent porosity in microporous polymer networks is
the result of extensive crosslinking reactions that prevent
the polymer chains from collapsing into a dense, nonporous
The construction of carbon–carbon and carbon–heteroa-
tom bonds by transition-metal-mediated organic processes
has become fundamental to the science of synthetic organic
chemistry in the past decades. In modern organic synthesis,
triphenylphosphine is an important ligand to noble metals in
carbon–carbon and carbon–heteroatom cross-coupling reac-
tion systems, for example, in the Wittig reaction,[13] the Mit-
sunobu reaction,[14] the Suzuki–Miyaura cross-coupling reac-
tion,[15] Mukaiyama–Corey lactonization,[16] the Appel reac-
tion,[17] and the Staudinger reaction.[18] Although homogene-
ous catalysts have been extensively investigated, their practi-
cal applications on a large scale remain challenging because
the catalysts are expensive and it is difficult to recover the
[a] Dr. Q. Zhang,+ Dr. Y. Yang,+ Prof. S. Zhang
Key Laboratory of Polymer Ecomaterials
Changchun Institute of Applied Chemistry
Chinese Academy of Science
Changchun 130022 (P.R. China)
Fax : (+86)430-85272117
E-mail: sbzhang@ciac.jl.cn
[b] Dr. Q. Zhang,+ Dr. Y. Yang+
Graduate School of Chinese Academy of Science
Beijing 100049 (P.R. China)
[+] These authors contributed equally to this work.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201300334.
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FULL PAPER
metal from the product. One approach that has been used
to address this issue of separation of the catalyst is to heter-
ogenize the metal catalyst by attaching it to a solid support.
A number of solid materials, such as carbon structures,[19]
polymers,[20] mesoporous silica,[21] and zeolites[22] have been
employed as supports for catalysts. Unfortunately, heteroge-
nizing the catalyst on a solid support often results in de-
creased activity.[23] Recently, microporous polymer networks
have emerged as a new class of attractive functional materi-
als.[12a,24] Due to their extraordinarily high surface area and
well-defined pore structure, microporous polymer networks
can be used as supports for catalytic systems.
FTIR analysis, whereby the disappearance of the C–Cl (n˜ =
750 cmÀ1) vibrations of the starting material indicated both
the complete consumption of monomers and the success of
phenyl–phenyl coupling (see Figure S1 in the Supporting In-
formation).
The PP P polymer was characterized by 31P solid-state
À
NMR analysis (Figure S2a). A signal at d=À9.2 ppm was
observed, corresponding to phosphorus in triphenylphos-
phine units, and a signal at d=25.2 ppm was assigned to
phosphorus in phosphine oxide units, which results from
aerobic oxidation of PIII. The integration ratio of signals
(phosphine oxide to phosphine atoms) was close to 1:20. In
31
À
In the present work, a porous polymer network with triva-
the P solid-state NMR spectrum of PP PO (Figure S2b),
À
lent phosphorus atoms as aromatic ring linkers (PP P) was
only a single peak was observed at d=24.7 ppm, which was
assigned to PV. Similar to other microporous polymers,[6] the
scanning electron micrograph revealed that samples are
composed of loose agglomerates of small particles with di-
ameters of approximately 200 nm (Figure S3). The polymers
were also stable towards water, base, and acid; indeed no
change in surface area was observed even after the material
was treated with 10m HCl. Thermal gravimetric analysis
(TGA) indicated that the polymer networks remained stable
up to 5008C (Figure S4).
synthesized by the homocoupling of tris(4-chlorophenyl)-
phosphine. The material exhibits a high surface area of
1284 m2 gÀ1 in the BET model and 1970 m2 gÀ1 in the Lang-
muir model. To the best of our knowledge, this is the first
report of a microporous organic polymer based on triphe-
nylphosphine unit. Palladium nanoparticles supported on
À
PP P have been prepared that exhibited extremely good
catalytic activity for Suzuki reactions. To investigate the role
À À
of the trivalent P atoms in the catalytic ability of PP P Pd,
the porous polymer network with phosphine oxide as aro-
Nitrogen adsorption–desorption isotherm measurements
À
matic ring linkers (PP PO) was also synthesized.
can be used to analyze the porous properties of microporous
polymers.[25,26] PP P and PP PO possess similar nitrogen
adsorption–desorption isotherms, which are combinations of
type I and II nitrogen sorption isotherms (Figure 1a) ac-
cording to IUPAC classification.[27] The high uptake at very
low pressures (0–0.1 bar) indicates a high microporosity.[20,28]
With increasing pressure, the nitrogen uptake increased
slightly, which indicates a little external surface area due to
the presence of very small particles.[20] These results suggest
À
À
Results and Discussion
Initially, two monomers were synthesized, as shown in
Scheme 1. The polymer networks were synthesized from
À
À
that PP P and PP PO have a predominantly microporous
structure in their framework.[27] Using a conventional flask
procedure, BET specific surface areas of 1284 m2 gÀ1 for
2
À1
À
À
PP P and 1353 m g for PP PO were obtained (Table 1).
Table 1. Porosity properties of microporous polymers.
[a]
[b]
[c]
Polymer SBET [m2 gÀ1
]
SLang [m2 gÀ1
]
V [cm3 gÀ1
]
VM [cm3 gÀ1
]
À
PP P
1284
1353
1970
2046
1.11
1.07
0.57
0.72
À
PP PO
[a] Specific surface area calculated from the nitrogen adsorption isotherm
by using the BET method. [b] Total pore volume at P/Po =0.97. [c] Mi-
cropore volume calculated from the nitrogen adsorption isotherm by
using the t-plot method.
Scheme 1. Synthesis of monomers and microporous polymers. TCP=
tris(4-chlorophenyl)phosphine, TCPO= tris(4-chlorophenyl)phosphine
oxide, cod=1,5-cyclooctadiene, bpy=2,2’-bipyridine.
these monomers through the Yamamoto reaction route.
These reactions produced off-white powdery compounds,
had a low density, and were not soluble in any common or-
ganic solvent. For purification, the sample was successively
immersed in water, ethanol, chloroform, and propan-2-one
to remove solvent residues and starting materials, and was
finally heated at 1208C for 12 h in vacuum to remove vola-
tile entities. The polymerization process was monitored by
The pore size calculated from nonlinear density functional
theory (NLDFT) gave a value of approximately 1.6 nm for
À
À
PP P and 1.5 nm for PP PO (Figure 1b). Recently, Cooper
and co-workers reported a series of nitrogen-containing mi-
croporous polymers based on poly(triethynylphenyl)a-
mine;[29] their material exhibited BET specific surface areas
in the range 500–1100 m2 gÀ1, which are a little lower than
those of our system. This result stems from two factors: dif-
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S. Zhang et al.
Figure 2. CO2 adsorption (closed) and desorption (open) isotherms at
273 K.
ciency, BPL carbon (SBET =1150 m2 gÀ1; a common reference
material for CO2 uptake) exhibited an uptake of
1.9 mmolgÀ1 at 1 bar and 273 K.[34] As an additional refer-
ence, the covalent organic framework, COF-102 (SBET
=
3620 m2 gÀ1) showed CO2 uptake of 1.56 mmolgÀ1 at 1 bar
and 273 K.[35]
Recently, microporous organic polymers with functional
groups have been found to have a broad range of potential
applications in heterogeneous catalyst systems due to their
large permanent surface area.[9b,36] In this work, because the
À
PP P polymer networks contain tertiary phosphines and
have a large surface area, their application as catalytic sys-
tems attracted our interest. Generally, polymer-supported
Figure 1. a) Nitrogen adsorption–desorption isotherms of microporous
polymer networks measured at 77 K. b) Pore-size distribution of micro-
porous polymer networks (adsorption and desorption branches are la-
beled with filled and open symbols, respectively).
Pd catalysts have been obtained by using [PdACTHUNTRGNE(UNG PPh3)4] as a
soluble Pd source.[15,37]
À
We immobilized Pd nanoparticles on PP P by a simple
À
ferent central link atoms (nitrogen and phosphine) and
monomer strut length.
impregnation of PP P with [Pd
N
temperature. Determination of the Pd content was carried
out by catalyst digestion followed by elemental analysis, and
the results are shown in Table S1 (see the Supporting Infor-
mation). The black solution lost all its color at a Pd/P molar
ratio of 1:1, whereas the polymer networks became a dark
black color. Inductively coupled plasma (ICP) analysis con-
firmed the loading of Pd on the PP P to be 11.2 wt%,
which corresponds to the complete absorption of Pd from
the solution. The Pd content of the PP P Pd can be readily
Adsorption processes for CO2 capture are essential today
in the context of mitigating the problems caused by global
warming from the emission of greenhouse gases.[30] Adsorp-
tion on porous solid media using pressure and/or tempera-
ture swing approaches is an emerging alternative that
should help to reduce the costs associated with the capture
step. The regeneration energy required for CO2 capture
using dry solid sorbent is significantly reduced, compared
with aqueous amine-based process.[31] For solid sorbents to
be competitive with existing amine-based scrubbing systems,
the CO2 adsorption capacity must be in the range of 3–
À
À À
controlled through the [PdACHTNUTRGNE(UNG PPh3)4] feed.
Generally, X-ray photoelectron spectra (XPS) allow the
valence and electron state change of atoms to be character-
ized. To investigate the coordination binding of Pd to the
phosphine ligand of the polymer network, we used XPS to
4 mmolgÀ1 of sorbent.[32] The PP PO network showed high
À
volumetric CO2 uptake of 3.83 mmolgÀ1 (1 bar and 273 K),
and the P-functionalized networks adsorbed less CO2
(2.46 mmolgÀ1), despite exhibiting similar surface areas
(Figure 2). The correlation between CO2 uptake and the sur-
face area is not proportional, and chemical functionality
also plays a role.[26,32,33] For our system, the phosphine oxide
À À
characterize the Pd valence state in PP P Pd and [Pd-
AHCTUNTGRENGUN(N PPh3)4]; the results are shown in Figure S5. It was found
that the Pd in the polymer networks exhibited the same
binding energy as that of [Pd(PPh3)4], which indicates the
phosphine ligand of the polymer networks coordinate to Pd.
AHCTUNGTRENNUNG
À
groups in PP PO may involve stronger interactions with
CO2 molecules than trivalent phosphorus and enhance CO2
adsorption capacity. As a comparison of the adsorption effi-
Figure 3 shows the transmission electron microscopy images
0
À À
of PP P Pd; the TEM analysis confirms that the Pd parti-
cles were uniformly dispersed in the polymer networks, and
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Microporous Organic Networks
FULL PAPER
Table 2. Suzuki cross-coupling reactions of aryl halides with phenylbor-
onic acid in the presence of different catalysts.
Entry
X
Y
Catalyst
Yield [%]
À À
1
2
3
4
5
6
7
8
I
H
H
H
H
PP P Pd
À À
PP P Pd
99.9
99.1
98.9
53.2
38.2
98.6
99.0
64.5
Br
Cl
Cl
Cl
Cl
Cl
F
À À
PP P Pd
À
À
PP PO Pd
H
[PdACTHUNGTRENNU(G PPh3)4]
À À
CH3
CHO
H
PP P Pd
À À
PP P Pd
À À
PP P Pd
À À
Figure 3. TEM images of PP P Pd. Scale bar: a) 10 nm and b) 5 nm.
that the average particle size was 3 nm. Larger Pd0 aggre-
lower activity (yield: 53.2%) compared with PP P Pd for
the coupling of 1-chlorobenzene and p-tolylboronic acid
under the same conditions (Table 2, entry 4). This result in-
dicates that the triarylphosphine improved the catalytic abil-
À À
À À
gates were not observed in PP P Pd, even when the weight
ratio of Pd to the polymeric scaffold was increased to 14%.
The crystal lattice of Pd0 was examined by high-resolution
TEM (Figure 3b), and the interplanar spacing was found to
be 0.27 nm. Generally, hypercrosslinked microporous poly-
mers show a relatively broad pore size distribution. The
À À
ity of PP P Pd.
À À
Most gratifyingly, when PP P Pd was used as a catalyst
for the reaction between fluorobenzene and p-tolylboronic
À
pore size distribution of PP P indicated the presence of mi-
acid, the coupling product was obtained in 64.5% yield. In
À
cropores (1–2 nm) and mesopores (2–4 nm), with the larger
Pd particles occupying the latter. Pd atoms in a nonaggrega-
tion state in the micropores were also detected by TEM-
general, catalytic C C cross-coupling reactions of fluoro-de-
[36]
À
rivatives are rare because of the strong C F bond. This
À À
superior catalytic performance of PP P Pd is presumably
À À
EDX in PP P Pd (Figure S6). The BET surface area de-
due to the structural features that allow incorporation of the
triarylphosphine inside the microporous structure. The re-
agents can be adsorbed into the porous channels by capillary
condensation of the micropores where the catalyst particles
are located. The concentration of reagents around the Pd
nanoparticles is higher than that in the bulk solution. The
small pore size (less than 2 nm) imposes a space confine-
ment effect on the reactants, leading to a high catalytic ac-
tivity. In addition, the triarylphosphine coordinated to the
active palladium sites had a profound influence on the cata-
lytic activity and stability of Pd0.[37] It is well-known that tri-
phenylphosphine-palladium complexes are widely used for
coupling reactions due to their excellent catalytic activity.[38]
For the practical application of a heterogeneous catalytic
system, its stability and reusability are important factors. For
metal-catalyzed reactions, including those involving palladi-
um, leaching of the noble metal is a major cause of catalyst
deterioration.[36] In this work, we have also examined the re-
creased from 1248 m2 gÀ1 (PP P) to 860 m g (PP P Pd:
9.8%) (Figure S7a), but no significant change in the pore
size was observed (Figure S7b).
2
À1
À
À À
As a model, we carried out Suzuki cross-coupling reac-
tions to evaluate the catalytic ability and recyclability of the
PP P Pd catalyst. To investigate the role of the oxidation
À À
À
À
À
state of the P atom in the catalytic ability of PP P, PP PO
Pd was also prepared. Due to environmental, economic, and
safety concerns, the Suzuki reactions were performed in
water with a suitable amount of EtOH used as a cosolvent
to increase the solubility of the substrates. The cross-cou-
pling reactions were carried out with 1 mol% Pd catalyst in
H2O/EtOH (3:1 v/v) at 808C. When the reaction was com-
plete, the reaction mass was extracted with diethyl ether
(10 mL), and the yield of the product was determined by
GC-MS analysis of the organic phase with dodecane as the
internal standard.
À À
À
As shown in Table 2, aryl iodides and bromides provided
the cross-coupling products in more than 99% yield. Using
both electron-rich and electron-deficient aryl chlorides with
cyclability and reusability of the PP P Pd catalyst. The PP
À
P Pd was readily recovered from the reaction mixtures
through simple filtration. The catalytic activity of the recov-
À À
À À
the PP P Pd system, the desired coupling products were
ered PP P Pd catalyst proved to be almost constant, with
obtained in high yields (more than 98%). This is significant,
because aryl chlorides are known to be sluggish coupling
partners.[35] The coupling yields for aryl chlorides, with some
recently reported catalytic systems based on Pd from other
groups as well as ours, were about 30%.[35] For comparison,
when the cross-coupling reaction between 1-chlorobenzene
the yield remaining within the range 99.1–97.2% after five
consecutive runs (Table S2). The filtrate was analyzed by
ICP-MS to estimate the palladium content and the results
revealed that approximately 31 ppb of palladium leached
into the solution, corresponding to an original metal loss of
0.005%, which is fifty times lower than the corresponding
value (0.27%) reported for Katoꢁs system.[36] No change in
and p-tolylboronic acid was carried out with [PdACHTNUTRGNE(UNG PPh3)4]
À
under the same conditions, a yield of 38.2% was obtained.
the chemical structure of the PP P polymer was detected by
On the other hand, when the Pd nanoparticles were incor-
31P solid-state NMR analysis after treatment with H2O/
V
À
porated on PP PO containing P , the material showed a
EtOH (3:1 v/v) at 808C for 100 h, which indicates that the
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S. Zhang et al.
polymer networks possess excellent stability. Thus, all the
Acknowledgements
À À
evidence demonstrates the durability of the PP P Pd cata-
This research was financially supported by the National Basic Research
Program of China (No. 2009CB623401 and 2012CB932802) and the Na-
tional Science Foundation of China (No. 51133008, 50825302, and
51021003).
lyst.
Conclusion
Phosphine and phosphine oxide functionalized microporous
organic networks were prepared by using Yamamoto type
cross-coupling reaction. The polymeric networks remained
stable up to 5008C and were also stable towards water, base,
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À
Polymerization for PP P: typical procedure: [Ni
N
8.18 mmol) was added to a solution of 1,5-cyclooctadiene (1.05 mL,
8.32 mmol) and 2,2’-bipyridyl (1.28 g, 8.18 mmol) in anhydrous DMF
(100 mL) and the mixture was heated at 808C for 30 min. Tris(4-bromo-
phenyl)phosphine (0.779 g, 1.57 mmol) was added to the resulting solu-
tion at 808C, and the mixture was stirred at that temperature for 10 h.
After cooling to RT, concentrated HCl (5m, 20 mL) was added to the sol-
ution. The solid obtained was filtered and the residue was successively
washed with H2O, EtOH, CHCl3, and propan-2-one. The polymer was
then dried in a vacuum oven at 1208C (83% yield).
Syntheses of polymer-supported palladium catalyst: Small portions of
[PdACHTUNGTRENNUNG(PPh3)4] were added at RT to a suspension of the polymer in anhy-
drous toluene under an argon atmosphere. The reaction mixture was de-
gassed with argon and stirred at RT for 20 h. The resin was filtered under
vacuum and washed three times with toluene and Et2O. The catalyst was
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Received: January 29, 2013
Published online: June 14, 2013
Chem. Eur. J. 2013, 19, 10024 – 10029
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10029