Turning on Catalysis: Construction of Triphenylphosphine Moieties into Porous Frameworks

Article abstract of DOI:10.1002/cctc.202000467

In this work, we present an effective strategy to enhance the reactivity and durability of molecular organometallic catalysts by constructing into porous frameworks, as demonstrated by triphenylphosphine (PPh₃). Such PPh₃ moieties accessible via the porous structures could be partially metalated by Pd species to generate a highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling of aryl chlorides. Site isolation in the rigid framework stabilizes the catalytically active monophosphine-ligated complex against deactivation into less active assemblies of bisphosphine-Pd. Meanwhile, the densely populated free ligands inhibit the decomposition of catalytically active sites thereby highlighting the beneficial effects of such a platform. Thus, the tunability of porous polymer synthesis gives great promise to impart numerous organometallic catalysts constituted by readily available ligands with unique reactivity, which are not trivially achievable with traditional systems.

Full text of DOI:10.1002/cctc.202000467

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Turning on Catalysis: Construction of Triphenylphosphine
Moieties into Porous Frameworks
Authors: Feng-shou Xiao, Fang Chen, Sai Wang, and Qi Sun
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To be cited as: ChemCatChem 10.1002/cctc.202000467
Link to VoR: https://doi.org/10.1002/cctc.202000467
01/2020

10.1002/cctc.202000467
ChemCatChem
FULL PAPER
Turning on Catalysis: Construction of Triphenylphosphine
Moieties into Porous Frameworks
Fang Chen,[a] Sai Wang,[a] Qi Sun,*[b] Feng-Shou Xiao*[a]
Dedication ((optional))
[a]
Mrs. F. Chen, Mr. S. Wang, Prof. F.-S. Xiao
Key Lab of Applied Chemistry of Zhejiang Province,
Zhejiang University
Tianmushan Road #138, Hangzhou 310007, China
E-mail: fsxiao@zju.edu.cn
[b]
Dr. Q. Sun
College of Chemical and Biological Engineering,
Zhejiang University
Zheda Road #38, Hangzhou 310027, China
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: In this work, we present an effective strategy to enhance
the reactivity and durability of molecular organometallic catalysts by
constructing into porous frameworks, as demonstrated by
triphenylphosphine (PPh3). Such PPh3 moieties accessible via the
porous structures could be partially metalated by Pd species to
generate a highly efficient and recyclable heterogeneous catalyst for
Suzuki coupling of aryl chlorides. Site isolation in the rigid framework
stabilizes the catalytically active monophosphine-ligated complex
against deactivation into less active assemblies of bisphosphine-Pd.
Meanwhile, the densely populated free ligands inhibit the catalytically
active sites from decomposition, thereby highlighting the beneficial
effects of such a platform. The tunability of porous polymer synthesis
thus gives great promise to impart numerous organometallic catalysts
constituted by readily available ligands with unique reactivity, which
are not trivially achievable with traditional systems.
catalytic site isolation in solid materials provides an alternative
route to prevent deleterious ligand exchanges, thus, stabilizing
the monophosphine-Pd intermediates in catalytic cycles. Also, the
incorporation of PPh3 moieties into a highly cross-linked polymer
backbone increases the steric hindrance of PPh3, facilitating
dissociation to a monophosphine adduct reminiscent of that from
using bulky ligands. Many fundamental concerns associated with
homogeneous catalysts, such as capital- and labor-intensive
ligand design in order to introduce steric hindrance for achieving
a monophosphine adduct and leaching of toxic metal species into
the products, can be overcome. Indeed, by virtue of site isolation
in solid materials, monophosphine-metal complexes have been
synthesized even by using less bulky ligands, which are
unachievable for the molecular counterparts.[6] Nonetheless,
these metal species are usually vulnerable under the catalytic
conditions, prone to decomposing into metal colloids. The use of
free ligands has proven to be useful to prevent such
decomposition. However, the excess free ligands in the solution
result in the metal species being locked up in a less active form.[7]
To tackle these issues, we postulated that constructing the
ligands into rigid porous materials, then partially metalated with
catalytic species might be a solution, given that the rigid
framework can effectively isolate the metal species while the
surrounded free ligands are conducive for improving the
resistance to the decomposition of immobilized complexes
(Figure 1). Recently, we showed that construction of the chiral
phosphoramidites into homochiral porous frameworks provided a
promising avenue to enhance the catalytic durability of the
molecular systems.[8]
Introduction
Phosphine-ligated transition metal complexes have been
essential to the development of organometallic chemistry.[1]
Among the developed reactions, the Suzuki coupling of aryl
halides with boronic acids is emerging as a favorite, which has
been applied industrially to the production of various compounds
ranging from drugs to materials.[2] However, for many years, a
significant limitation of this transformation has been the poor
reactivity of aryl chlorides, which, from the viewpoint of availability,
is more attractive than the corresponding bromides and iodides.[3]
In order to facilitate such transformations, bulky ligands are
necessary as their steric demand facilitates ligand dissociation to
afford highly reactive palladium complexes with only one ligand,
which initiates the catalytic cycles.[4] Hurdles that impede their
practical application mainly include the cumbersome synthesis of
these ligands, along with their homogeneous nature, which
complicates the product recovery and catalyst reuse. Alternative
systems are thus desired to engender reactivity of heterogeneous
systems toward the Suzuki coupling of aryl chlorides.[5]
To test our hypotheses, triphenylphosphine (PPh3) was the
ligand of our choice, as it constitutes one of the panthea of
privileged ligands in the current scenario of organometallic
catalysis, and has been proved to be inactive in the Suzuki
couplings of aryl chlorides.[3a] This contribution describes details
of our studies on the coordination properties of porous polymeric
PPh3 toward Pd2+ complexes and its catalytic application to
Suzuki coupling of aryl chlorides. Initial investigations revealed
that the loading amount of Pd species has a significant impact on
the number of coordinating phosphines with Pd species and the
Given the importance of achieving monophosphine ligation for
producing an aryl chloride Suzuki catalyst, we envisaged that
1
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10.1002/cctc.202000467
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FULL PAPER
durability of the resulting catalysts. Our work highlights the use of
the rigid framework as a tool for producing highly active catalyst
species rather than merely to have the benefit of easy separation,
reuse, and recycling of the catalyst.
compared to the pristine POL-PPh3 (1116 m2 g-1) are consistent
with the presence of Pd species in the pores. As a representative
sample, POL-PPh3 metalated with 5.0 wt.% Pd species is
Figure 1. Schematic illustration of turning on reactivity due to the formation of
catalytic active monophosphine-ligated Pd2+ complex in the porous polymeric
triphenylphosphine, while forming less active bisphosphine-ligated complex and
decomposing of catalytic species in the homogeneous catalysis.
Results and Discussion
Figure 2. Solid-state 31P NMR spectra. 31P signals at -6.1, 24.8, and 30.4 are
assignable to the free PPh3, bisphosphine-ligated Pd2+ complex, and
monophosphine ligated complex, respectively.
The porous polymeric PPh3 (POL-PPh3) was prepared by the free
radical polymerization of tris(4-vinylphenyl)phosphine, according
to the procedures reported by our groups.[9] The resulting material
is a highly porous amorphous polymer with excellent thermal
stability (Figures S1-S4). Treatment of POL-PPh3 with
PdCl2(PhCN)2 in various ratios afforded the catalysts with different
illustrated thoroughly. This material showed a BET surface area
of 919 m2 g-1, with the pore size distribution centered at 20 nm
(Figure 3a and Figure S6). High-resolution transmission electron
microscopy (HRTEM) images revealed that the Pd species were
highly dispersed in the material (Figure 3b), and no aggregated
particles were observed, which were further validated by the
energy dispersive X-ray (EDX) mapping (Figures 3e-3h). The
interactions between the PPh3 moieties and Pd species were
verified by the XPS spectra, which revealed that the P 2d binding
energy of this material (131.7 eV) exhibited a higher value than
that of the pristine POL-PPh3 (130.4 eV, Figure 3c), while the
binding energies at 337.4 and 342.6 eV, attributable to the Pd2+
palladium loading amounts, which were denoted as
x
wt.%Pd/POL-PPh3 (x stands for the mass ratio of palladium in the
resulting materials). The content of Pd species was determined
by inductively coupled plasma-optical emission spectroscopy
(ICP-OES), which revealed that they were very close to the
theoretical values. These results suggested that the metalation
proceeded in a quantitative yield. The color of the resulting
catalysts ranged from light yellow to orange with the Pd content
increase. The appearance of Pd signals in the X-ray
photoelectron spectroscopy (XPS) spectra of x wt.%Pd/POL-
PPh3 indicates the successful metalation with Pd species.[10] The
solid-state 31P NMR analysis supported the formation of both
monophosphine ligated andbisphosphine-ligated Pd2+ complexes,
with their ratio increasing along with the Pd species content
increase (Figure 2 and Figure S1). In contrast, the corresponding
homogeneous systems of PPh3 and PdCl2(PhCN)2 gave
bisphosphine-ligated complex as a single product, irrespective of
the stoichiometry of PPh3 and PdCl2(PhCN)2. This is not
surprising as the rigid framework could work against the free
ligand exchange, stabilizing the monophosphine-Pd complex. On
the other hand, the densely populated PPh3 moieties result in
partially cooperative binding, especially when there are far more
ligands than Pd species in the materials. To evaluate the porosity
of these catalysts, N2 sorption isotherms were collected at -196 °C,
and all of them are high porosity with Brunner−Emmet−Teller
(BET) surface areas in the range of 730-1074 m2 g-1 (Table 1 and
Figure S5). The smaller surface areas of metalated polymers
Table 1. The ratio of PPh3 moieties and Pd species, BET surface areas of
various Pd metalated POL-PPh3, and the corresponding catalytic activity in the
Suzuki coupling of 4-chlorotoulene and phenylboronic acid.[a]
Catalyst
Pd loading[b] P/Pd[c]
BET (m2 g-1)
1074
995
Yield[d]
14.3
18.6
32.1
78.8
67.6
0.5 wt.% Pd/POL-PPh3
1.0 wt.% Pd/POL-PPh3
2.5 wt.% Pd/POL-PPh3
5.0 wt.% Pd/POL-PPh3
0.5 (0.49)
1.0 (1.01)
2.5 (2.47)
5.0 (4.98)
60/1
30/1
12/1
5.5/1
957
919
10.0 wt.% Pd/POL-PPh3 10.0 (9.75) 2.5/1
730
[a]4-Chlorotoluene (1.0 mmol), phenylboronic acid (1.1 mmol), K3PO4·3H2O (2.0
mmol), toluene/water (4 mL/1 mL), catalyst (0.5 mol%, based on Pd species),
80 C for 1 h. [b]Theoretical Pd weight percent in the resulting catalysts. The
values in parentheses refer to the Pd weight percent evaluated by ICP-OES.
[c]The ratio of PPh3 moieties and Pd species in the resulting catalysts. [d]The
yields were determined by gas chromatography (GC).
2
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10.1002/cctc.202000467
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Figure 3. (a) N2 sorption isotherms of 5.0 wt.%Pd/POL-PPh3 collected at -196 °C. (b) HRTEM image of 5.0 wt.%Pd/POL-PPh3. (c and d) XPS spectra. (e-h) HADDF-
TEM image and corresponding elemental mapping of 5.0 wt.%Pd/POL-PPh3.
3d5/2 and Pd2+ 3d3/2, respectively, which are lower than those of
PdCl2(PhCN)2 (337.9 and 343.2 eV, Figure 3d). The interaction
between Pd species and PPh3 moieties in POL-PPh3 was further
supported by the appearance of double peaks at 508 cm-1 and
524 cm-1, characteristic absorption of Pd-P stretching vibration
bands (Figure S7). The appearance of the 31P NMR signal at 29.4
ppm confirmed the formation of the monophosphine ligated Pd2+
complex.[4e, 5c]
activities of 5.0 wt.% Pd/POL-PPh3 and 10.0 wt.% Pd/POL-PPh3
at a higher S/C ratio of 2000. Their difference in catalyst durability
was clearly manifested in the reactivity profiles. In the presence
of 5.0 wt.% Pd/POL-PPh3, the conversion proceeded linearly with
time until it was approaching completion. 10.0 wt.% Pd/POL-PPh3
showed activities at low conversion that were comparable to that
of 5.0 wt.% Pd/POL-PPh3. However, diminished efficiency was
detected as the reaction proceeded (Figure 4). These results
imply the importance of the existence of dense free ligands in
close proximity to active sites in order to boost their durability, and
consequently, the accompanying efficiency.
After confirming the formation of mono-ligation, to explore their
applicability toward Suzuki coupling of aryl chlorides, we set out
to evaluate their performance in the coupling of 4-chlorotoluene
and phenylboronic acid. Screening experiments revealed that the
coupling gave the highest efficiency when K3PO4·3H2O and the
mixture of toluene and H2O (V/V=4/1) were base and reaction
medium, respectively (Table S1). As expected, Pd complexes,
formed by the combination of PPh3 and various Pd precursors,
including PdCl2(PhCN)2, PdCl2, Pd(OAc)2, Pd2(dba)3, and PdCl2,
did not induce the reaction, offering the product in less than 1.0%
yields (Table S2). By contrast, the resulting metalated POL-PPh3
are all active in this transformation to give the corresponding biaryl
product (Table S3). At a S/C ratio of 200 (S/C, the molar ratio of
reagent to Pd), 5.0 wt.% Pd/POL-PPh3 provided a complete 4-
chlorotoluene conversion within 2 h at 80 °C, outperforming all the
other catalysts tested. Assessment of the catalytic responses of
these materials was displayed in Table 1, showing that the ratio
of PPh3 moiety and Pd species had a significant impact on the
catalytic activity. Upon an increase of the ratio of Pd species with
PPh3 moieties in the polymer, with the Pd species content
increase from 0.5 wt.% to 5.0 wt.%, augmented productivity was
observed, in line with the monophosphine-ligated Pd content in
the resulting material. As the Pd content further increased from
5.0 wt.% to 10.0 wt.%, the biaryl product yield decreased from
78.8% to 67.6%, which, however, was contradicted by the
proportion of catalytically active species in them. We reasoned
that the discrepancy in the yields might be related to their
difference in stability, as the color change gradually from orange
to brown during the course of the reaction, which was observed
for 10 wt.% Pd/POL-PPh3, signaling the occurrence of catalyst
decomposition. To validate this assumption, we compared the
Figure 4. Time-resolved profiles for the yield of biaryl product in the Suzuki
coupling of 4-chlorotoulene and phenylboronic acid. Reaction conditions: 4-
chlorotoluene (10 mmol), phenylboronic acid (11 mmol), K3PO4·3H2O (20 mmol),
toluene/water (8 mL/2 mL), catalyst (0.05 mol%, based on Pd species), 80 C.
To provide additional evidence, we decreased the density of
PPh3 moieties by the copolymerization of divinylbenzene (DVB)
with tris(4-vinylphenyl)phosphine to give a porous polymer with a
PPh3 concentration of 0.5 mmol g1 (BET: 827 m2 g-1, Figure S8).
After coordinating with PdCl2(PhCN)2, the resulting catalyst
3
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10.1002/cctc.202000467
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[a]Reaction conditions: aryl chlorides (1.0 mmol), phenylboronic acid (1.1 mmol),
K3PO4·3H2O (2.0 mmol), toluene/water (4 mL/1 mL), catalyst (0.5 mol%, based
(Pd/PDVB-PPh3, wherein the ratio of PPh3 moieties to Pd is about
1 and the Pd content in the resulting material is 4.9 wt.%) afforded
the biaryl product in only 13.7% conversion after 2 d, after which
no further conversion was observed with further heating (Figure
4). Considering that Pd/PDVB-PPh3 and 5.0 wt.% Pd/POL-PPh3
possess a similar density of active sites and surface areas, the
significant difference in the stability further confirms the role of
free ligands arranged around the catalytic species. These ligands
surrounded the active sites are expected to repair broken metal-
ligand bonds during catalysis continuously, thereby enhancing the
durability of the catalyst.
on Pd species), 80 C for
1
h. [b]The yields were determined by gas
chromatography. [c]Recycle for 10 times.
To clarify the actual active species, a set of poisoning tests
were carried out. Considering that the catalytic activity of 5.0 wt.%
Pd/POL-PPh3 was not influenced by the presence of poly(4-vinyl
pyridine) (6% cross-linked, PVPy), a known trapper for the “naked”
Pd0 species, this species can, therefore, be excluded from the
catalytic cycle (Figure S13).[11] The addition of Hg0 led to a
decrease in activity, indicating that Pd0 species were involved in
the catalytic cycle (Figure S13).[12] Given that XPS and TEM
analyses have revealed that Pd particles are undetectable in 5.0
wt.% Pd/POL-PPh3 after the reaction, we thus speculated that
Pd0Lx was most likely the active species. In combination with
characterization results, Pd0PPh3 is the active species to initial the
catalytic cycle, although more in-depth investigations of the
mechanisms are necessary.
Knowing the optimized conditions, we explored the scope of the
Suzuki coupling. A wide array of electronically and structurally
diverse aryl chlorides and arylboronic acids can be cross-coupled
efficiently. As summarized in Table 2, a broad spectrum of aryl
chlorides can be coupled cleanly with phenylboronic acid over 5.0
wt.% Pd/POL-PPh3, including extremely electron-rich aryl
chlorides 4-chloroanisole and 4-chloroaniline. Also, sterically
hindered aryl chlorides, such as 2-chlorotoluene and 2-
chlorobenzonitrile, were also suitable substrates, thus
demonstrating the broad applicability of this system. It is worth
mentioning that the efficiency of the developed catalytic system in
terms of turnover frequency (TOF) is among the top compared
with the reported systems (see Table S4).
To gain insight into the fate of these catalysts, the surface
states of Pd species after the reaction were monitored by XPS
and TEM measurements. Obvious Pd colloids were detected for
Pd/PDVB-PPh3 and 10.0 wt.% Pd/POL-PPh3, indicative of the
occurrence of catalyst decomposition under the catalytic
conditions to generate catalytically inactive Pd species (Figures
S9 and S10). In contrast, no detectable aggregated Pd species
were observed for 5.0 wt.% Pd/POL-PPh3 (Figure S11).
Additionally, after separation of the catalysts, the Pd species in
the filtrate were undetectable for 5.0 wt.% Pd/POL-PPh3, implying
that there is almost no Pd leaching. However, 5.8% and 14.7% of
Pd species were leached into the supernatant for 10.0 wt.%
Pd/POL-PPh3, and Pd/PDVB-PPh3, respectively. The above
results prove that the free ligands in the catalyst also act as
reservoirs to prevent the Pd species from leaching. Moreover, no
further conversion was detected after removal of 5.0 wt.%
Pd/POL-PPh3, suggestive of the heterogeneous nature of the
reaction. Upon completion of the reaction, the catalyst could be
readily recovered by centrifugation and reused for the next cycle
without loss of activity. Such a process can be maintained at least
10 times (Table 2, entry 2 and Figure S12). It is worth mentioning
that Pd particles immediately precipitated out after mixing the
reactants with PdCl2(PPh3)2, and a large number of Pd particles
were also formed when nonporous polymerized PPh3 was used
as support. These results collectively indicate the importance of
porosity and a high concentration of PPh3 species for preventing
catalytically active species from decomposing and leaching, thus
enabling long-term durability.
Conclusion
In summary, we introduce porous polymeric ligand as a platform
to enhance the reactivity and durability of molecular
organometallic catalysts. The synergistic combination of site
isolation and surrounded free ligands to impart the catalytically
ineffective homogeneous analog PdCl2(PPh3)2 with superior
performance in the Suzuki coupling of aryl chlorides. The
systematic material library and relationships identified between
active species and free ligand content suggest general
structure−property criteria design improved catalysts with high
efficiency and durability.
Table 2. Substrate scope of the Suzuki coupling with phenylboronic acid over
5.0 wt.% Pd/POL-PPh3.[a]
Entry
Substrate
Time (h)
Yield (%)[b]
>99.5
96.1
TOF (h-1)
100
96
1
2
Acknowledgements ((optional))
2[c]
3
2
The authors acknowledge laboratory and equipment mangement,
Zhejiang University (SJS201801), as well as the the National
Science Foundation of China (21720102001, 91634201, and
21673205), National Key Research and Development Program of
1.5
2
>99.5
>99.5
98.3
133
100
49
4
5
4
China (2017YFB0702803).
6
2.5
>99.5
80
Keywords: porous frameworks • phosphine-ligated Pd complex
• Suzuki coupling • monophosphine ligation • heterogeneous
catalysis
7
8
0.5
0.5
>99.5
99.1
400
400
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Turning on catalysis: The construction of PPh3moieties into porous frameworks leads to dramatic acceleration of the Suzuki coupling
of aryl chlorides, whereas, the molecular analogs have no activity. The isolation of active sites on rigid frameworks allows the formation
of catalytically active monophosphine ligated Pd species. The arrangement of free ligands in the vicinity of active sites enables a very
efficient self-healing system.
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