Bis-N,N-aminophosphine (PNP) crosslinked poly(p-tert-butyl styrene) particles: A new support for heterogeneous palladium catalysts for Suzuki coupling reactions

Article abstract of DOI:10.1016/j.catcom.2019.105715

Crosslinked polymer particles carrying hemilabile bis-N,N-aminophosphine (PNP) moieties are obtained by the copolymerization of a PNP-derived monomer bearing four vinyl fragments as cross-linkers, with para-tert-butylstyrene and divinylbenzene, using free radical copolymerization in presence of AIBN, performed in aqueous dispersed medium. This new support was characterized by thermogravimetric analysis, elemental analysis, laser diffraction, solid state NMR. The PNP moiety could allow monochelation to palladium. The resulting insoluble Pd-catalyst revealed to be very active for Suzuki cross-coupling with several substrates, allowing separation of the product from the catalyst by filtration. The final palladium PS-PNP catalyst could be reused for several catalytic cycles.

Full text of DOI:10.1016/j.catcom.2019.105715

Accepted Manuscript
Bis-N,N-aminophosphine (PNP) crosslinked poly(p-tert-butyl
styrene) particles: A new support for heterogeneous palladium
catalysts for Suzuki coupling reactions
Vito Vece, Kai C. Szeto, Marc O. Charlin, Pascal Rouge, Aimery
De Mallmann, Manel Taam, Pierre-Yves Dugas, Muriel Lansalot,
Franck D'Agosto, Mostafa Taoufik
PII:
S1566-7367(19)30177-3
https://doi.org/10.1016/j.catcom.2019.105715
105715
DOI:
Article Number:
Reference:
CATCOM 105715
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
24 March 2019
27 May 2019
28 May 2019
Please cite this article as: V. Vece, K.C. Szeto, M.O. Charlin, et al., Bis-N,N-
aminophosphine (PNP) crosslinked poly(p-tert-butyl styrene) particles: A new support
for heterogeneous palladium catalysts for Suzuki coupling reactions, Catalysis
Communications, https://doi.org/10.1016/j.catcom.2019.105715
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ACCEPTED MANUSCRIPT
Bis-N,N-aminophosphine
(PNP)
crosslinked
poly(p-tert-butyl
styrene) particles: A new support for heterogeneous palladium
catalysts for Suzuki coupling reactions
Vito Vece, Kai C. Szeto, Marc O. Charlin, Pascal Rouge, Aimery De Mallmann, Manel Taam,
Pierre-Yves Dugas, Muriel Lansalot, Franck D’Agosto, Mostafa Taoufik*
Université Lyon 1, Institut de Chimie de Lyon; CPE Lyon; CNRS, UMR 5265 C2P2, Bâtiment
3
7
08 F 43 Blvd du 11 Novembre 1918 F-69616, Villeurbanne Cedex, France. Fax: (+33) (0)4
2 43 17 95; E-mail: taoufik@cpe.fr.
Abstract:
Crosslinked polymer particles carrying hemilabile bis-N,N-aminophosphine (PNP) moieties
are obtained by the copolymerization of a PNP-derived monomer bearing four vinyl
fragments as cross-linkers, with para-tert-butylstyrene and divinylbenzene, using free radical
copolymerization in presence of AIBN, performed in aqueous dispersed medium. This new
support was characterized by thermogravimetric analysis, elemental analysis, laser
diffraction, solid state NMR. The PNP moiety could allow monochelation to palladium. The
resulting insoluble Pd-catalyst revealed to be very active for Suzuki cross-coupling with
several substrates, allowing separation of the product from the catalyst by filtration. The
final palladium PS-PNP catalyst could be reused for several catalytic cycles.
Keywords: Free radical polymerization; aqueous dispersed media; C-C coupling; catalyst
recycling

ACCEPTED MANUSCRIPT
1
. Introduction
The formation of the C–C bond is among the most useful synthetic transformations to
conceive fine chemicals, pharmaceuticals, and agrochemicals [1]. In this field, catalytic
Suzuki-Miyaura (S-M) coupling of aryl halides with arylboronic acids has become the
dominant synthetic scheme. This technique is very efficient and easy to perform due to the
stability toward air and non-toxicity of boronic acids used during this reaction [2, 3]. It has
also found new applications for the preparation of advanced materials within optics and
electronics [4]. Palladium is among the most applied element in the S-M coupling, under the
form of soluble monometallic species derived from Pd(II) or Pd(0) complexes [5-9]. Several
studies have suggested that the formation of colloidal nanoparticles can act as catalyst or,
more likely, as precursor of the active species [10, 11]. On the other hand, uncontrollable
growth of these aggregates will inevitably lead to the formation of insoluble black palladium,
responsible of the deactivation during the C-C coupling reaction. In order to avoid this
problem, tailored ligands are used to increase the stability of the catalyst and to trigger the
reaction for less reactive substrates. However, these Pd catalysts are usually air sensitive,
expensive, difficult to obtain and not available commercially. To resolve these problems,
development of heterogeneous catalysts based on palladium is highly needed for practical,
economic and environmental reasons [12-14]. Other advantages are the possibility of
recovery and recycling of the solid catalyst, being crucial in view of up-scaling at industrial
level. In addition, working with a supported Pd-catalyst offers the opportunity to conduct
the reaction under continuous flow mode [15]. Different strategies have been used to obtain
Palladium-based heterogeneous catalysts for C–C coupling reactions [3]. Compared to both
inorganic or organic-inorganic supports [16], a rather promising approach is based on
palladium(II) complexes grafted into organic polymer particles. Owing to their strong -
donating ability and high versatility, phosphines [17, 18] and diphosphines [19] have been
incorporated into organic polymer particles and the resulting products used as supports in
heterogeneous transition metal catalysis [20, 21]. Among all the polymers that have been
used to carry the Pd source, polystyrene (PS) incorporating phosphine ligands was
extensively studied in particular, due to a ligand mobility as in homogeneous catalysis [22,
23]. Various heterogeneous systems have been developed to catalyze different chemical
transformations such as alkylation [24], C-N bond formation [25] and the Suzuki cross
coupling [16]. In many cases, using flexible linear polymer chains causes unfavorable steric
environment around the Pd-active sites, resulting in deactivation and in reduced catalyst
performances. Thus, it is crucial to incorporate a designed phosphine ligand on the PS
backbone in order to increase the activity of Suzuki-Miyaura coupling. A fairly recent
approach is to introduce a cross-linking mono-phosphine agent during the polymerization of
styrenic monomers leading to the increase of the density of polystyrene chains around the
phosphine center, and thereby reduce multidentate P-coordination to the metal [22]. This
mono-phosphine functionalized crosslinked polymer particles can readily coordinate to

ACCEPTED MANUSCRIPT
palladium complexes and offer a stable and more active heterogeneous catalyst for S-M
coupling and selective head-to-head dimerization of farnesene [26]. Furthermore, the
insoluble Pd-catalyst obtained by this new strategy can easily be separated from the reaction
crude by filtration. However, this catalyst gradually degrades upon several regeneration
cycles by leaching of the metal due to low stability of the mono-coordinated Pd center. The
same group has further extended their work on biphosphine ligand based on 1,2-
bis(diphenylphosphino)benzene grafted into crosslinked polymer particles to further
stabilize the active metal center [27]. This material has been used in amination of
arylchloride and C-H/C-O coupling after functionalization with Ni, and alkene hydroboration
after functionalization with Cu or Co. Extensive analyses for the metal coordination have
revealed the importance of a monochelated system, as offered by the 1,2-
bis(diphenylphosphino)benzene, compared to other bisphosphine ligands allowing multi-
chelating systems. However, neither the S-M reaction nor recycling experiments were
further investigated. Another strategy for the stabilization of active center is to use
tridentate “pincer” ligands. In fact, these ligands provide a unique balance of versatility,
stability and reactivity in organometallic chemistry and catalysis. The development of pincer
PNP ligands has led to many applications in catalysis, including facile chemical
transformations at transition metal centers with high stability during catalysis [28]. However,
the catalytic activity of these systems with palladium is generally low probably due to the
formation of bis-chelated single metal complexes or multinuclear complexes [27]. Herein,
we report the synthesis of the first example of coordinated Palladium catalyst to PNP ligand-
based cross-linked poly(para-tert-butyl styrene) (PS) particles obtained by free radical
copolymerization performed in an aqueous dispersed medium. This is achieved by using an
original soluble tetra-vinylated PNP ligand. The resulting support will be used for Suzuki type
coupling reactions, catalyzed by Pd isolated center, leading to diphenyl compounds. The Pd-
PNP-PS catalyst could be recycled demonstrating a good stability and recyclability of this
new material during the S-M coupling catalytic process.
2
. Experimental
2.1. Synthesis of (methylamino)-bis[di(4-ethenylphenyl)phosphine] (PNP monomeric ligand)
(
5).
A 5 mL solution of bromostyrene (2.0 g, 10.9 mmol, 4 eq) was added to an excess of
Mg dissolved in THF at -20 °C. After 3h, the bromostyrene magnesium was filtrated by a
cannula and transferred into another Schlenk containing a solution of MeNP2Cl4, 2, (648 mg,
2.73 mmol, 1.0 eq) [29] dissolved in 3 mL THF and maintained at -20 °C. The reaction was
stirred for 1 h at -20 °C and then at room temperature during 3 h. The solution was
quenched by addition of deionized water (5 mL). Precipitate was filtrated and the liquid was
extracted by dichloromethane. The combined organic phases were dried with MgSO4,
filtered and concentrated. The crude product was purified by chromatography (Eluent:
pentane/ethyl-acetate = 98/2 to pentane/ethyl-acetate = 93/7) to give 415 mg of PNP ligand

ACCEPTED MANUSCRIPT
1
3
5
(1.64 mmol, yield = 61%). NMR H (ppm, CD2Cl2): 2.53 (3H, (t), J = 3.0Hz, H1), 5.39 (4H, (d),
3
3
3
3
J = 11.1Hz, H3a), 5.92 (4H, (d), J = 17.4Hz, H3b), 6.84 (4H, (dd), J = 17.7Hz, J = 11.1Hz, H2),
.36 - 7.63 (16H, (m), HAr). NMR C (ppm, CD2Cl2): 31.77, 113.66, 125.19, 131.72, 135.49,
37.13, 137.17. NMR P (ppm, CD2Cl2): 71.89.
1
3
7
1
3
1
2.2. Synthesis of PNP-PS crosslinked particles (6).
A solution of NaCl (3.0 g) in water (120 mL) with acacia gum (4.8 g) was placed in a two-neck
flask equipped with a magnetic stirring bar and deoxygenated by purging with Argon. On the
other hand, a solution of para-tert-butylstyrene (5.5 mL, 30.0 mmol), divinylbenzene (72 L,
0.50 mmol) and PNP ligand, 5, (250 mg, 0.5 mmol) dissolved in chlorobenzene (6 mL) was
rapidly injected into the aqueous solution under stirring. Azobisisobutyronitrile (AIBN) (98.5
mg, 0.60 mmol) was then added to this medium and the mixture was kept at 95 °C under
stirring (24h). The reaction was then stopped by cooling at room temperature and the solid
obtained was isolated by filtration under a reduced pressure, washed successively with
water (700 mL), MeOH (600 mL), THF (600 mL) and toluene (600 mL) and then dried under
vacuum at 90 °C for 24h in order to give the desired polymer as white beads (4.0 g).
2.3. Synthesis of Pd-PNP-PS (7).
In a glovebox, the PNP and crosslinked PS particles 6 (0.5 g) were heated using a sand bath
and contacted with a solution of Pd(acac)2 (45 mg) in toluene at 70 °C during 4 h. The
resulting suspension was filtrated and washed successively with toluene and pentane. The
powder was dried under vacuum and stored in the glovebox.
2.4. General procedure for a Suzuki-Miyaura coupling reaction
To a mixture of aryl halide (0.52 mmol), arylboronic acid (0.75 mmol), potassium phosphate (1.49
mmol) and solid catalyst, 7 (1,43 mol % Pd) was charged degassed THF (3 mL). The mixture was
pumped and refilled with nitrogen three times. The resultingmixture was stirred at 60℃ under argon
for 15 h, and then cooled to room temperature, portioned with water (5 mL) and ethyl acetate (5
mL). The solid was filtrated, washed with water and ethyl acetate. The organic layer was separated,
dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to
provide biaryl compounds.[30, 31]
3
. Results and discussions

ACCEPTED MANUSCRIPT
Scheme 1: Synthesis of PNP monomeric ligand 5 in two steps from methylamino
hydrochloride
An adaptable monomeric ligand should contain the following criteria: i) PNP moiety;
ii) styrene fragment suitable for radical polymerization; iii) preferable sterical demand with
moderate P-P proximity in a pyramidal-type space to facilitate the chelating effect and
accessibility of the substrate. The simplest ligand satisfying the aforementioned criteria is
depicted in Scheme 1 (5). However, this molecule has never been reported before. For the
synthesis of this new tetravinylated PNP ligand 5, methylamino hydrochloride, 1 and
phosphorus trichloride are first brought together to reflux in 1,1,2,2-tetrachloroethane to
give the phosphorus substituted amine, 2 (Scheme 1) [29]. Each of the four chlorine atoms
was then substituted by an aryl group using styrene magnesium bromide, 4, generated from
commercially available bromostyrene, 3. This led to the PNP ligand bearing four styrene
units, obtained after purification with reasonably good yield (61%). It has been observed that
5
shows a small tendency to polymerize at room temperature and needs therefore to be
1
31
13
kept cold. The material was then characterized by H (Fig. A.1), P (Fig. A.2) and C NMR
3
1
1
(
Fig. A.3) to validate the structure ( P NMR (CD2Cl2): 71.9 ppm) [32]. H NMR in CD2Cl2 of the
PNP ligand, 5, shows two doublets at 5.39 and 5.92 ppm and a quadruplet at 6.84 ppm
characteristic of the vinyl group of styrene fragment necessary to prepare the PNP-
functionalized PS beads by free radical copolymerization.
Scheme 2: Synthesis of PNP-PS ligand and Pd-PNP-PS

ACCEPTED MANUSCRIPT
The tetravinylated PNP ligand, 5, was successif copolymerized in the presence of
divinylbenzene (DVB) used as crosslinker in order to obtain more homogeneous and very
uniform polymer beads [22], para-tert-butylstyrene (60 equivalents with respect to 5), and
acacia gum in a saturated aqueous solution containing a soluble amount of chlorobenzene.
The polymerization was initiated with AIBN after a prolonged degassing under argon and
heating at 95 °C. At the end of the polymerization, a solid, 6, was harvested by filtration and
thoroughly dried. The average volume equivalent sphere diameter D[4,3] is found to be 80.8
µm by laser diffraction (Fig. A.4, Table A.1). The polymer particles obtained are then smaller
than those of monophosphine crosslinked PS triphenylphosphane particles (300-400 µm)
reported by Iwai et al. [22]. The thermogravimetric analysis (Fig. A.5) of the dried PNP cross-
1
linked PS showed that the organic support is highly stable (no weight loss below 250 °C). H
NMR spectrum (Figure 1) displayed two broad signals at 1.2 ppm (typically aliphatic CH, CH2
and CH3 groups from polystyrene and tert-butyl fragment) and 7.0 ppm (aromatic protons).
1
3
C NMR (Fig. A.6) showed several resonances localized at 31.3 and 33.9 ppm (originated
from para-tert-butyl fragment), 39.4 and 44.8 ppm (usually observed for a polystyrene
backbone, attributed to CH2 and CH in between two aromatic cycles), 120.6-133.1 ppm
(
attributed to carbons from aromatic fragment). Finally, 31P NMR spectrum (Figure 1)
displayed an intense signal at 71.2 ppm, indicating that its electronic and steric properties
3
1
are virtually the same as in the monomer 5 ( P NMR: δ 71.9 ppm) and confirming the
successful incorporation of the PNP units into the crosslinked PS matrix. The phosphorus
-1
loading value ([P] = 0.16 mmol g ) was determined by elemental analysis. Dried material was
then swollen with toluene in order to allow the grafting of (Pd(acac)2) on the PNP moieties of
the polymeric material. The catalyst changed color and turned as expected from white to
orange after the coordination of palladium.
*
*
14
12
10
8
6
4
2
0
-2
-4
140
120
100
80
60
40
20
0
-20
1
31

( H) / ppm
 ( P) / ppm
1
31
Figure 1: H (500 MHz) and P (202.4 MHz) NMR spectra of the polymeric support
containing methyl N,N-bis(diarylphosphino) moieties (10 kHz; *: spinning side bands).
1H and 13C Solid state NMR characterizations of the Pd-coordinated PNP-
functionalized and crosslinked PS gave virtually the same spectra as its Pd-free homologue
3
1
(
Fig. A.7, Fig. A.8). However, no P NMR signal was detected in different acquisition modes

ACCEPTED MANUSCRIPT
(
CP MAS, 31P{H} with different relaxation times). Only very weak resonances corresponding
to the un-coordinated phosphorous was observed after very long accumulation (Fig. A.9).
3
1
Absence of P NMR signal is probably due to a combination of broadening of the peak and
reduced mobility of phosphorous when Pd is coordinated. On the other hand, elemental
analysis revealed that the concentration of phosphorus (0.48 wt%) and palladium (0.53 wt%)
-1
-1
in the lattice, corresponds to [P] = 0.15 mmol g and [Pd] = 0.05 mmol g . The observed
Pd/P ratio of ⅓ suggesting that 2/3 of the PNP fragment has coordinated to Pd, indicates
that there are still un-coordinated phosphine moieties in the material, which is also
confirmed by solid state 31P NMR. The deficit of Pd concentration may be due to the
inaccessibility of few PNP groups in the polymeric structure. In addition, IR spectroscopy
-1
reveals appearance of a new peak at 1583 cm (Figure A.10), which corresponds to typical
(C=O) vibration in acetylacetonate, suggesting successful coordination of Pd(acac) complex

2
onto the support.
We then chose to explore the use of such Pd-coordinated polymeric beads toward
the Suzuki-Miyaura coupling of unactivated bromoarenes. For S-M reactions, the importance
of the mono-ligation of two electron donor ligands has been established using electron rich
phosphane [33, 34] and N-heterocyclic Carbenes ligands [35] in order to perform the
catalytic reaction.
Scheme3: The Suzuki couplingreactions of para-bromotoluene with phenylboronicacidsusing the
polymer supported methyl amino N,N-bis(diarylphosphino) ligand.
The supported palladium complex was evaluated as precatalyst in the Suzuki reaction of
para-bromotoluene with selected phenylboronic acids (Scheme 3). Following optimization of
the reaction, a palladium loading of 7.5 mol was employed together with K3PO4 as the base
in THF at 60 °C. Control experiments showed that in the absence of the catalyst no reaction
took place. However, in the presence of the catalyst (1.4 mol%), para-bromotoluene reacts
cleanly with phenylboronic acids to give the appropriate cross-coupling products, generally
in high yield (Table 1). As expected, the yields of the coupling product in reactions of para-
bromotoluene with phenylboronic acids presenting a highly electron withdrawing group
(
CF3) or an important steric hindrance are lower. Current material also couple chloro-toluene
with selected arylboronic acid efficiently (Table 1) with similar conversion as the highly
reactive bromotoluene.

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Table 1. Suzuki-Miyaura cross-coupling reaction of para-
a
b
bromotoluene and para-chlorotoluene with phenylboronic acid
derivatives using the Pd supported complex as catalyst.
Boronic acid
Phenylboronic Acid
% Conversion % Isolated Yield
a
98
99
100
100
99
87
60
99
84
84
86
92
50
22
84
87
87
91
95
99
91
95
81
54
96
68
73
66
84
47
15
79
79
80
a
(
(
o)-Tolylboronic Acid
m)-Tolylboronic Acid
a
a
(
(
p)-Tolylboronic Acid
p)-Ethylphenylboronic Acid
2)-Methoxyphenylboronic Acid
3)-Trifluoromethylphenylboronic Acid
4)-Methoxyphenylboronic Acid
4)-Vinylphenylboronic Acid
3)-Fluorophenylboronic Acid
4)-Fluorophenylboronic Acid
4)-Ethoxycarbonylphenylboronic Acid
a
a
(
(
(
(
(
(
(
(
(
a
a
a
a
a
a
a
a
2,4,6)-Trimethylphenylboronic Acid
2,4,6)-Triisopropylphenylboronic Acid
b
Phenylboronic Acid
b
(
(
p)-Tolylboronic Acid
2)-Methoxyphenylboronic Acid
b
Reaction conditions: THF, 0.15 g of the polystyrene supported Pd precatalyst,
.5 µmol Pd (1.43 mol% Pd), 1.49 mmol K3PO4, 0.75 mmol ArB(OH)2, 0.52
7
mmol PhBr, 60 °C, 15 h. Conversion of para-bromotoluene and Chlorotoluene
1
determined by H NMR analysis.
The supported palladium complex could be easily filtrated and reused at least six times for
the coupling reaction of para-bromotoluene with phenylboronic acid, leading to 4-methyl-
1,1'-biphenyl, without important decrease of activity between two runs.
Table 2. Suzuki-Miyaura cross-coupling reaction of para-
bromotoluene with phenylboronic acid using the Pd supported
a
complex as catalyst and reusing it.
Run
% Conversion
% Isolated Yield
1
2
3
4
5
6
(first use)
98
95
92
92
98
97
91
80
87
78
87
94
a
Reaction conditions: THF, 0.15 g of the polystyrene supported Pd precatalyst,
7
.5 µmol Pd (1.43 mol% Pd), 1.49 mmol K3PO4, 0.75 mmol C6H5B(OH)2, 0.52
1
mmol PhBr, 60 °C, 15 h. Conversion of para-bromotoluene determined by H
NMR analysis.
Importantly, no evident physical change of the Pd-coordinated PNP-functionalized and
crosslinked PS, such as a black color, was observed after multiple recycling experiments,
indicating the absence of metallic Pd. Moreover, no loss of activity was observed, strongly
suggesting the absence of leaching. Hence, the PNP-functionalized polymer particles
synthesized in this study seem to have/show enhanced stability compared to the previously
published mono-coordinated Pd triphenylphosphine crosslinked PS particles [22].

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4
. Conclusion
In conclusion, a novel organic molecule bearing PNP-moiety and styrene fragments has been
synthesized and characterized. This molecule can readily be polymerized through free radical
polymerization performed in an aqueous dispersed medium to achieve micrometric polymer
particles bearing bis(phosphino)amine functionality. This material can serve as support for
heterogeneous catalysis. Indeed, it has been demonstrated that palladium can be
coordinated to the PNP fragment, leading to a very efficient precatalyst for C–C coupling
reactions in the Suzuki reaction. Moreover, it can be easily isolated from the reaction
medium by filtration after reaction and could be reused at least five times without decrease
of activity.
Acknowledgement
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the online version, at doi:
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Highlights
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Novel ligand comprising PNP moiety and 4-fold styrene fragment is presented
Crosslinked polymer particles carrying PNP are obtained by radical polymerization
The crosslinked polymer particles can be used as support to immobilize Pd-complexes
The materials were used as recyclable heterogeneous catalysts for C-C coupling