Porous organic polymer supported rhodium as a reusable heterogeneous catalyst for hydroformylation of olefins

Article abstract of DOI:10.1021/acs.orglett.9b00459

A new porous organic polymer has been prepared via copolymerization of divinyl-functionalized phosphoramidite ligand and tris(4-vinylphenyl)phosphine. The porous polymer was loaded with Rh(acac)CO₂ to yield a supported Rh catalyst, which demonstrated good regioselectivity (l/b = 6.7-52.8) and high catalytic activity (TON up to 45.3 × 10⁴) in hydroformylation of terminal and internal olefins. Remarkably, the heterogeneous catalyst can be reused at least 10 cycles without losing activity and selectivity in hydroformylation of 1-hexene.

Full text of DOI:10.1021/acs.orglett.9b00459

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Porous Organic Polymer Supported Rhodium as a Reusable
Heterogeneous Catalyst for Hydroformylation of Olefins
Xiaofei Jia,*,†,§ Zuyu Liang,†,§ Jianbin Chen,‡ Jinhe Lv,† Kai Zhang,† Mingjie Gao,† Lingbo Zong,*,†
and Congxia Xie*,†
†Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular
Engineering, Qingdao University of Science and Technology, Qingdao 266042, P. R. China
‡Shandong Provincial Key Laboratory of Molecular Engineering, School of Chemistry and Pharmaceutical Engineering, Qilu
University of Technology (Shandong Academy of Sciences), Jinan 250353, P. R. China
S
* Supporting Information
ABSTRACT: A new porous organic polymer has been
prepared via copolymerization of divinyl-functionalized
phosphoramidite ligand and tris(4-vinylphenyl)phosphine.
The porous polymer was loaded with Rh(acac)CO2 to yield
a supported Rh catalyst, which demonstrated good regiose-
lectivity (l/b = 6.7−52.8) and high catalytic activity (TON up
to 45.3 × 104) in hydroformylation of terminal and internal
olefins. Remarkably, the heterogeneous catalyst can be reused
at least 10 cycles without losing activity and selectivity in hydroformylation of 1-hexene.
ydroformylation, developed by Roelen in the 1930s, is the
loading the metals. In 2015, Xiao reported a Rh-dppe-POP
Hmost cost-effective industrial processes for synthesis of catalyst, which provided excellent yields and selectivities for
linear aldehydes in hydroformylation of olefins.9 Phossphite/
PPh3 copolymer developed by Yan and Ding was successfully
used for hydroformylation of terminal and internal olefins.10
However, the development of novel heterogeneous hydro-
formylation catalyst with high catalytic activity and good
reusability still remains a challenge. It is well-known that PPh3
and bisphosphoramidite ligands11 were widely used in hydro-
formylation of olefins. Using PPh3 constructed a stable porous
organic polymer, while more efficient bisphosphoramidite
ligand was added by copolymerization. The porous organic
polymer not only has the advantages of PPh3 and bi-
sphosphoramidite ligands but also reduces the loss of metal
due to high concentration of ligands. Herein, we report a new
Rh-loaded porous organic ligand (Rh/POL-BPa&PPh3),
bearing both pyrrolyl-based bisphosphoramidite (BPa) and
triphenylphosphane ligand moieties, as a heterogeneous catalyst
for hydroformylation of terminal and internal olefins. Because of
high π-acidity of the N-pyrrolylphosphorus unit,11 stable PPh3
moieties, and high ligand density, the heterogeneous catalyst
exhibited excellent activity, regioselectivity, and recyclability in
the hydroformylation of olefins.
aldehydes.1 As versatile chemical intermediates, more than 10
million metric tons of aldehydes are produced every year.2
Because of the good catalytic activity and selectivity,
homogeneous ligand-modified Rh catalysts were successfully
used in industrial hydroformylation. However, the heteroge-
neous catalysts often present significant advantages over
homogeneous catalysts in terms of recyclability and catalyst
separation.3 In the past decades, many types of solids were used
as supporting materials for immobilizing homogeneous hydro-
formylation catalysts, including various inorganic porous
materials (such as SiO2, zeolites and activated carbons)4 and
organic polymers (such as polystyrene, chitosan, and cyclo-
dextrin).5 Despite notable achievements, these traditional
supported catalysts are often plagued by leaching of metals,
decrease of catalytic activity, and/or loss of selectivity,
presumably owing to the low concentration of ligands
coordinated to the metals.
In recent years, porous organic polymers (POPs) have
attracted great attention, not only due to their high surface areas
but also to the incorporation of various functionalities within
their porous structures.6 As POPs constructed from organic
ligand-containing monomers, porous organic ligands (POLs)
feature a high density of ligand sites, which would improve
loading capability and stability of the active metals and thus to
enhance the catalytic activity and selectivity and to reduce the
loss of metals in a catalytic process.7 In recent years, Xiao, Ding,
et al. developed Rh/POL-PPh3 and Rh/phosphite-POP
catalysts, which demonstrated high activity and excellent
recyclability in hydroformylation of olefins.8 As the monomers,
bisphosphorus ligands were also used to construct polymers for
Our initial effort was focused on the synthesis of the
comonomers 6 and 7. The divinyl-functionalized bisphosphor-
amidite 6 (vBPa) were readily synthesized by using a five-step
reaction sequence. As shown in Scheme 1, 2,2′-biphenol 1 was
reacted with Br2 to produce dibrominated product 2, which was
diacetylated to 3 on treatment with acetyl chloride. Pd-catalyzed
Received: February 3, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b00459
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 1. Synthesis of POL-BPa&PPh3 and BPa
Figure 1. (a) 13C MAS NMR spectrum, (b) 31P MAS NMR spectrum,
(c) TGA curve, (d) N2 sorption isotherms, (e) SEM image, (f) TEM
image of Rh/POL-BPa&PPh3.
Suzuki coupling reaction of 3 with potassium ethenyltrifluor-
oborate yielded 4, which underwent a base-mediated hydrolysis
to give the key intermediate divinyl-functionalized biphenol 5.
The divinyl-functionalized ligand monomer 6 was prepared by
treatment of diphenols 5 with chlorodipyrolyphosphine in the
presence of Et3N. On the other hand, (4-vinylphenyl)-
magnesium bromide was reacted with PCl3 to produce
trivinyl-functionalized ligand monomer 7 (3vPPh3). AIBN
initiated copolymerization of vinyl-functionalized bisphosphor-
amidite 6 and tris(4-vinylphenyl)phosphine 7 (3vPPh3) in THF
afforded the copolymer POL-BPa&PPh3 as a light-yellow solid.
Subsequent treatment of the copolymer with Rh(acac)(CO)2 in
THF solvent readily furnished Rh-loaded copolymer Rh/POL-
BPa&PPh3 as a yellow solid (for details, see the Supporting
Information (SI)). For comparison purposes, bisphosphorami-
dite ligand 8 (BPa) and 9 (POL-PPh3) were also prepared.
The obtained Rh/POL-BPa&PPh3 was characterized by
inductively coupled plasma mass spectrometry (ICP-MS),
solid NMR, thermogravimeric analysis (TGA), N2 adsorp-
tion−desorption analysis, scanning electron microscopy (SEM),
and transmission electron microscopy (TEM). ICP-MS
indicated a rhodium loading of 0.71 wt % (Rh:vBPa:3vPPh3 =
1:3:27) in the material. In the 13C MAS NMR spectrum of Rh/
POL-BPa&PPh3, two groups of peaks centered at 127.0 and 40.6
ppm can be assigned to the aromatic carbons and polymerized
vinyl groups, respectively (Figure 1a). The 31P MAS NMR
spectrum exhibited two peaks at −7.4 and 64.9 ppm,
corresponding to the phosphorus signals of polymerized
vPPh3 and vBPa moieties, respectively. Remarkably, the peak
at 26.1 ppm was attributed to the P atoms of polymerized vPPh3
coordinated to Rh, while two peaks at 107.4 and 97.4 ppm in
low-field can be assigned to phosphorus of polymerized vBPa
coordinated to Rh (Figure 1b). The polymeric material Rh/
POL-BPa&PPh3 showed good thermal stability according to
thermogravimetric analysis (TGA), giving only 5% weight loss
upon heating to 200 °C and significant decomposition started
around 370 °C (Figure 1c). Furthermore, the nitrogen sorption
isotherm (Figure 1d) demonstrated that Rh/POL-BPa&PPh3
has a hierarchical porosity, which is further confirmed by
scanning electron microscopy (Figure 1e) and transmission
electron microscopy (Figure 1f). The pore sizes of Rh/POL-
BPa&PPh3 are mainly distributed around 1.2−2.0 and 2.3−25
nm, which is based on the calculations of nonlocal density
functional theory (NLDFT), indicating that Rh/POL-
BPa&PPh3 mainly consists of micro- and mesopores (for
details, see the SI). The Brunauer−Emmett−Teller (BET)
surface area and pore volume of Rh/POL-BPa&PPh3 are as high
as 423.6 and 0.41 m3/g, respectively, which should be beneficial
for its application as a catalyst because diffusion of reactants and
products would be facilitated in the reaction processes.
The catalytic performance of Rh/POL-BPa&PPh3 was
evaluated in the hydroformylation of olefins, initially using 1-
hexene as model substrate. Several reaction parameters, e.g.,
temperature, pressure of syngas, and reaction time, were
investigated. As shown in Table 1, although the conversion of
1-hexene increased with the temperature increment 80−100 °C,
a higher temperature (100 °C) resulted in lower regioselectivity
toward the linear aldehyde and an enhancement of hydro-
genation product (Table 1, entries 1−3). As expected, the
pressure of syngas displayed a significant effect on hydro-
formylation. Either increasing the H2/CO pressure from 10/10
to 20/20 bar, or decreasing H2/CO pressure to 5/5 bar, led to a
decline in catalytic activity (Table 1, entries 4, 5 vs 2). Reaction
time was also found to be crucial for hydroformylation of 1-
hexene. In the initial stage of the reaction (1 h), the TON value
was determined to be quite high (2.3 × 104, Table 1, entry 6).
The conversion of 1-hexene improved with the increasing
reaction time, and similar hydrogenation and isomerization
reaction results were observed (Table 1, entries 2 and 6−9). The
efficiency of different homogeneous ligands in Rh-catalyzed
hydroformylation of 1-hexene was also investigated. In
B
DOI: 10.1021/acs.orglett.9b00459
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
Table 1. Catalytic Hydroformylation of Olefins
b
c
d
e
entry
catalysts
substrate
H2/CO (bar)
temp (°C)
t (h)
conv (%)
l/b
linear
[H] (%)
iso (%)
TON
1
2
3
4
5
6
7
8
9
10
11
12
13
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BPa&PPh3
Rh/POL-BP&PPh3
Rh/POL-BPa&PPh3
Rh/BPa
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-hexene
1-octene
2-octene
10/10
10/10
10/10
5/5
80
90
100
90
90
90
90
90
90
90
90
90
90
90
110
5
5
5
5
5
1
2
3
4
5
5
5
5
5
15
83.3
90.3
92.0
82.8
73.8
75.7
80.2
81.9
85.4
99.0
68.9
83.5
61.9
80.0
34.1
50.1
25.4
54.7
43.5
46.3
51.6
45.0
49.1
15.7
2.9
97.2
98.0
96.2
98.2
97.7
97.9
98.1
97.8
98.0
94.0
74.5
98.7
76.5
97.6
87.0
5.3
6.2
9.2
5.1
2.9
4.3
5.0
4.7
4.2
0.9
0.8
2.9
1.4
0.7
4.5
5.9
6.0
7.3
4.9
2.6
4.3
5.2
5.2
5.1
3.0
0.4
3.3
2.1
8.0
2.5 × 104
2.7 × 104
2.8 × 104
2.5 × 104
2.2 × 104
2.3 × 104
2.4 × 104
2.5 × 104
2.6 × 104
3.0 × 104
2.1 × 104
2.5 × 104
1.9 × 104
1.6 × 104
0.6 × 104
20/20
10/10
10/10
10/10
10/10
10/10
10/10
10/10
10/10
10/10
10/5
f
g
Rh/PPh3
Rh/BPa/PPh3
Rh/POL−PPh3
Rh/POL-BPa&PPh3
h
75.5
3.3
41.0
6.7
i
j
14
15
k
Rh/POL-BPa&PPh3
62.2
0.0
a
b
c
5.0 mg catalyst, 1-hexene (1.5 mL), S/C = 30000, decane as the internal standard. Linear/branched aldehyde ratio. Percentage of linear
aldehyde in all aldehydes. Hydrogenation to alkane. Isomerization to 2-alkene. Rh(acac)(CO)2:Bpa = 1:3, S/C = 30000. Rh(acac)(CO)2:PPh3
= 1:27, S/C = 30000. Rh(acac)(CO)2:Bpa:PPh3 = 1:3:27, S/C = 30000. 3.0 mg catalyst, 1-hexene (1.5 mL), S/C = 30000. 5.0 mg catalyst, S/C
= 20000. 5.0 mg catalyst, S/C = 10000.
d
e
f
g
h
i
j
k
comparison with Rh/POL-BPa&PPh3, Rh/PPh3 gave a
substantially lower regioselectivity and catalytic activity, whereas
Rh/BPa afforded higher TON value and slightly lower l/b ratio
(Table 1, entries 2 vs 10, 11). Adding excess free PPh3 to Rh/
BPa catalyst resulted in higher regioselectivity (Table 1, entries
12 vs 10). We assumed that high concentration of PPh3 ligands
coordinated with Rh-Bpa complexes, affording high steric
hindrance catalytic intermediate, leading to superior regiose-
lectivity in the hydroformylation process. Rh/POL-PPh3 was
also tested in this reaction, affording a lower regioselectivity
(Table 1, entries 13 vs 2). On the basis of the above results, we
concluded that the heregeneous Rh/POL-BPa&PPh3 catalyst
could afford similar regioselectivity and catalytic activity
compared with its homogeneous counterpart (Table 1, entries
2 vs 12). BPa ligand moieties were more favorable for improving
catalytic activity and regioselectivity than PPh3 moieties, and the
synergetic effect of PPh3 and BPa moieties with Rh species
probably contributed to high regioselectivity.10b Under
optimized reaction conditions, longer chain 1-octene was
readily amenable to the Rh/POL-BPa&PPh3 catalyzed hydro-
formylation procedure, affording excellent linear/branched
ratios (l/b = 41.0). Furthermore, a modest TON value and l/b
ratio were achieved in the isomerization-hydroformylation of 2-
octene (Z/E = 3.6/1), owing to PPh3 moieties in the catalyst
reducing the isomerization rate of 2-octene to 1-octene.
To evaluate the activity of a catalyst, the substrate/catalyst (S/
C) ratios were surveyed in Rh/POL-BPa&PPh3 catalyzed
hydroformylation of 1-hexene under optimized reaction
conditions (CO/H2 = 10/10 bar, T = 90 °C, 5 h) (Table 2).
Increasing the S/C ratio from 3 × 104 to 50 × 104 resulted in a
considerable enhancement of TON value (from 2.7 × 104 to
18.4 × 104) in 5 h reaction time, while the chemo- and
regioselectivites were well retained. Under substrate/catalyst
ratio of 50 × 104, conversion of 1-hexene in 24 h was increased to
90.5%, albeit at a cost of slightly lower regioselectivity. It is
noteworthy that such a high activity is rare for a heterogeneous
hydroformylation catalyst and hence might be a valuable
attribute for further practical development.
Table 2. Substrate/Catalyst (S/C) Ratios Screening for
Hydroformylation of 1-Hexene
a
d
e
conv.
(%)
[H]
iso.
b
c
entry
S/C
l/b
linear
(%)
(%)
TON
1
2
3
3 × 104
90.3
78.5
50.0
43.0
36.7
90.5
50.1
50.2
52.8
25.1
43.9
12.1
98.0
98.0
98.1
96.2
97.8
92.4
6.2
6.9
9.6
7.7
3.3
11.0
6.0
7.2
6.6
5.5
4.1
16.4
2.7 × 104
3.9 × 104
5.0 × 104
8.6 × 104
18.4 × 104
45.3 × 104
5 × 104
10 × 104
20 × 104
50 × 104
50 × 104
f
4
f
5
g
6
a
Reaction conditions: 5.0 mg Rh/POL-BPa&PPh3, CO/H2 = 10/10
b
c
bar, T = 90 °C, 5 h. Linear/branched aldehyde ratio. Percentage of
d
linear aldehyde in all aldehydes. Hydrogenation to alkane.
e
f
g
Isomerization to 2-alkene. 3.0 mg Rh/POL-BPa&PPh3. 3.0 mg
Rh/POL-BPa&PPh3, 24 h.
Reusability of Rh/POL-BPa&PPh3 was evaluated in hydro-
formylation of 1-hexene. Under optimized conditions, Rh/POL-
BPa&PPh3 catalyst preserved high activities and excellent
chemo- and regioselectivites during its 10 reruns, highlighting
its excellent reusability (SI). As shown in Figure 2, similar results
demonstrated that the catalyst has excellent stability and
reusability. After each run, the catalyst was recovered via
centrifugal separation. The supernatant liquid showed no
activity in hydroformylation of 1-hexene, thus confirming the
heterogeneous nature of the catalysis. Meanwhile, Rh leaching in
the residual liquids was determined to be ∼0.1 ppm by ICP-MS
analysis. The results indicated that the Rh leaching from the Rh/
POL-BPa&PPh3 is negligible, probably owing to the high
density of ligands in the catalyst.
In conclusion, a new porous organic polymer (POL-
BPa&PPh3) was synthesized through copolymerization of
divinyl-functionalized phosphoramidite ligand and trivinyl-
functionalized triphenylphosphane. The rhodium-loaded poly-
meric material, Rh/POL-BPa&PPh3, was successfully used as a
C
DOI: 10.1021/acs.orglett.9b00459
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
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heterogeneous catalyst in hydroformylation of terminal and
internal olefins, affording high l/b ratios (6.7−52.8) and
excellent TON values (up to 45.3 × 104). Remarkably, the
heterogeneous catalyst was also reused for 10 cycles in
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.orglett.9b00459.
Experimental procedures, analytical data, and NMR
spectra (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
*X.J.: E-mail, jiaxiaofei139@163.com.
*L.Z.: E-mail, lingbozong@qust.edu.cn.
*C.X.: E-mail, xiecongxia@126.com.
ORCID
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X.; Chen, W.; Ding, Y.; Li, J.; Xiao, F.-S. Chem. Commun. 2014, 50,
11844. (b) Sun, Q.; Aguila, B.; Verma, G.; Liu, X.; Dai, Z.; Deng, F.;
Meng, X.; Xiao, F.-S.; Ma, S. Chem. 2016, 1, 628.
(9) Sun, Q.; Dai, Z.; Liu, X.; Sheng, N.; Deng, F.; Meng, X.; Xiao, F. S.
J. Am. Chem. Soc. 2015, 137, 5204.
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Xiaofei Jia: 0000-0002-5306-0395
Author Contributions
§Xiaofei Jia and Zuyu Liang contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge financial support from the Natural Science
Foundation of Shandong Province (no. ZR2016BQ24) and
Natural Science Foundation of China (no. 21703116,
51702180).
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DOI: 10.1021/acs.orglett.9b00459
Org. Lett. XXXX, XXX, XXX−XXX