Styrene Hydroformylation with In Situ Hydrogen: Regioselectivity Control by Coupling with the Low-Temperature Water–Gas Shift Reaction

Article abstract of DOI:10.1002/anie.202000998

The hydroformylation of olefins is one of the most important homogeneously catalyzed industrial reactions for aldehyde synthesis. Various ligands can be used to obtain the desired linear aldehydes in the hydroformylation of aliphatic olefins. However, in the hydroformylation of aromatic substrates, branched aldehydes are formed preferentially with common ligands. In this study, a novel approach to selectively obtain linear aldehydes in the hydroformylation of styrene and its derivatives was developed by coupling with a water–gas shift reaction on a Rh single-atom catalyst without the use of ligands. Detailed studies revealed that the hydrogen generated in situ from the water–gas shift is critical for the highly regioselective formation of linear products. The coupling of a traditional homogeneous catalytic process with a heterogeneous catalytic reaction to tune product selectivity may provide a new avenue for the heterogenization of homogenous catalytic processes.

Full text of DOI:10.1002/anie.202000998

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Accepted Article
Title: Styrene Hydroformylation with In situ H: Regioselectivity Control
by Coupling with Low-temperature Water Gas Shift Reaction
Authors: Botao Qiao, Tianbo Li, Fang Chen, Rui Lang, Hua Wang,
Yang Su, Aiqin Wang, and Tao Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202000998
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10.1002/anie.202000998
Angewandte Chemie International Edition
COMMUNICATION
Styrene Hydroformylation with In situ Hydrogen: Regioselectivity
Control by Coupling with Low-temperature Water-Gas Shift
Reaction
Tianbo Li,[a,c] Fang Chen,[a] Rui Lang,[a] Hua Wang,[a] Yang Su,[a] Botao Qiao,*[a] Aiqin Wang,[a] Tao
Zhang*[a,b]
Dedicated to the 70th anniversary of Dalian Institute of Chemical Physics, CAS
Abstract: Hydroformylation of olefins is one of the most important
Wilkinson’s catalyst prefers the production of branched
homogeneously catalyzed industrial reactions for aldehyde synthesis. aldehydes rather than linear ones [2]. It was suggested that the
Various ligands are usually used to obtain desired linear aldehydes
in aliphatic olefin hydroformylation. However, in aromatic
hydroformylation it prefers to obtain branched aldehydes with
common ligands, posing a grand challenge for the synthesis of linear
products. In this work a novel approach to selectively obtain linear
aldehydes in hydroformylation of styrene and its derivatives was
realized by coupling with a water-gas shift reaction on Rh single-
atom catalyst without using ligands. Detailed studies revealed that
the in situ H generated from the water-gas shift plays a critical role in
determining the high regioselectivity to linear products. The coupling
formation of a stable benzylic Rh-species induced by the η2
electron donation from the benzene ring might contribute to this
unusual regioselectivity, [3] as illustrated in scheme 1 (C⇌D→E).
To obtain high selectivity to linear aldehyde, steric hindrance
ligands, such as triphosphoramidite and tetradentate phosphine,
have to be used, with which linear/branched aldehyde (l : b) ratio
of about 3 in styrene hydroformylation was achieved.[4] However,
although these special ligands can give rise to linear products,
the high cost and complex synthetic procedure severely limited
their practical applications. Therefore, the development of new
approaches to manipulate the regioselectivity of styrene
hydroformylation remains attractive but challenging in both
fundamental study and practical applications.
of
a
traditionally homogeneous catalysis process with
a
heterogeneous catalysis reaction to tune product selectivity may
provide a new avenue for the heterogenization of homogenous
catalysis process.
In hydroformylation reaction, besides the main reaction to
produce aldehyde, hydrogenation of C=C double bond could be
one of the side reactions which usually occurs upon Rh complex
aggregating into Rh nanoparticles (NPs). Single-atom catalyst
(SAC) was recently reported to be chemoselective without C=C
hydrogenation side product[5]. Meanwhile heterogenization of
homogenous catalysis process through SAC has attracted more
and more attention.[6] On the other hand, in situ generated H
(denoted as in situ H) was popularly used in the field of selective
hydrogenation.[7] There were also a few literatures about using
alcohol or polylol[8] to substitute for H2 in hydroformylation
catalyzed by homogeneous Rh-based compounds, but hydrogen
were provided as ex-situ H2 rather than in situ H, and the C=C
double bond hydrogenation product were observed.
Hydroformylation of olefins is one of the most important
homogeneously catalyzed industrial reactions for aldehyde
synthesis. Phosphorus (P) ligand modified Rh compounds are
widely used as catalysts.[1] In general, a high excess of ligands
is required to stabilize the Rh complex and to suppress the
undesired branched aldehydes. Studies about regioselectivity of
hydroformylation are mostly focused on ligands’ development
and optimization.
Styrene is an unusual class of substrate that favors
producing branched aldehyde with traditionally common ligands.
For instance, Wilkinson’s catalyst is widely used in
hydroformylation of chain olefins to produce linear aldehydes.
However, hydroformylation of styrene and its derivatives on
In this work, we report a new approach to selectively obtain
linear aldehyde in styrene hydroformylation through
a
heterogeneous catalysis process without using any ligands, i.e.,
by using a CeO2 supported Rh SAC coupled with a low-
temperature water gas shift (LWGS) reaction to produce in situ
H. With this new route, in addition to avoiding hydrogenation of
styrene and phenylpropyl aldehyde the ratio of n-aldehyde to
isoaldehyde is, surprisingly, as notable as 3. Therefore, this
coupling route suggests a promising new way to produce linear
aldehyde in hydroformylation of styrene and its derivatives
without using complex ligands.
[a]
T. Li,[+] Dr. F. Chen,[+] Dr. R. Lang, Dr. H. Wang, Y. Su, Prof. B.
Qiao,* Prof. A. Wang, Prof. T. Zhang*
Dalian Institute of Chemical Physics
Chinese Academy of Sciences
Dalian 116023 (China)
E-mail: bqiao@dicp.ac.cn
taozhang@dicp.ac.cn
Prof. T. Zhang*
[b]
[c]
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023 (China)
T. Li
CeO2 supported Rh SAC (denoted as Rh1/CeO2) and Rh NP
catalyst (denoted as 5Rh/CeO2) with nominal Rh loadinig of 0.5
wt% and 5 wt%, respectivley, were synthesized through a
feasible electrostatic adsorption method. Thanks to the high Ce
vacancy density of the synthesized CeO2 the loading for SAC is
relativley high.[9] For comparison, CeO2 supported Rh NPs with
same loading to Rh1/CeO2 (0.5 wt%, denoted as NP-Rh/CeO2)
University of Chinese Academy of Sciences
Beijing 100049, China
[+] These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.202000998
Angewandte Chemie International Edition
COMMUNICATION
was also prepared by deposing colloidal Rh NPs onto the CeO2
surface. The particle size of both NP catalsyts was about 3 nm,
as shown in Figure S1. Metal loadings measured by inductively
coupled plasma optical emission spectrometer (ICP-OES) show
that the actual loading is similar to the nominal ones for all
catalysts.
CO together with the lack of coverage-dependent shift of the
linear Rh-CO demonstrates that Rh atoms are singly dispersed
and isolated from each other[5, 13, 15] (Figure S3a). In addition, the
angle between the dicarbonyl groups was calcluated to be 92o
(see details in SI), further comfirming the isolated nature of the
15b]
isolated Rh atoms.[5,
For NP-Rh/CeO2 and 5Rh/CeO2
catalysts, two and three peaks are distinct which can be
attributed to bridged-CO adsorption (1860 cm-1 or 1800 cm-1)
and linear-CO adsorption on Rh0 (2046 cm-1), respectively,
Figure 1d. The 1960 cm-1 peak on 5Rh/CeO2 may be asscoiated
the CO adsorption on Rh-CeO2 interface.[16] Notably, upon
helium purging a red-shift of the linear Rh-CO is clearly
observed (Figure S3b). This phenomenon, together with the
presence of bridged-CO species, provides strong evidence of
Rh NPs. Therefore, according to the combination of DRIFT
spectra of CO adsorption and microscopy study, we can safely
conclude that Rh SAC and Rh nanocatalyst were successfully
constructed.
Rh
1
a
b
2081
2010
2052
2200 2100 2000 1900 1800 1700
Wavenumber(cm-1)
NP-Rh
d
c
5Rh
2046
1860
1800
1960
Table 1. Hydroformylation of styrene with different catalysts.a
×1/100
2200 2100 2000 1900 1800 1700
Wavenumber(cm-1)
Figure 1. Aberration-corrected HAADF-STEM images of Rh1/CeO2 (a) and
NP-Rh/CeO2(c); DRIFT spectra of CO adsorption at 25 °C on Rh1/CeO2 (b),
NP-Rh/CeO2 (d red line) and 5Rh/CeO2 (d blue line). The DRIFT spectra were
collected after CO adsorption for 10 min and He purging for 10 min.
Entry
Catalysts
Conv
/%
Sel of Ald[f]
/%
Sel of Alc[g]
/%
l/b
1[a]
2[b]
3[c]
4[d]
5[a]
6[a]
7[e]
Rh1/CeO2
Rh1/CeO2
RhCl(PPh3)3
Rh1/CeO2
NP-Rh/CeO2
RhCl3
79
99
99
0
98
72[h]
96
-
2
0
3
-
3.0
0.9
0.4
-
Examination of Rh1/CeO2 by aberration corrected scan
transmission electron microscopy (STEM) which guarantees a
sub-angstrom resolution reveals that no Rh NPs and/or subnano
clusters were observed in both high and low magnification
images, suggesting an atomic dispersion of the Rh species,
Figure 1a and S2. Although STEM images do not exclusively
disclose the presence of Rh single atoms on account of the low
Z contrast between Rh and Ce, the EDS measurement (Figure
S2) do evidence the homogenously dispersed Rh species,
confirming the presence of invisible atomically dispersed Rh. On
the other hand, for NP-Rh/CeO2 sample the low magnification
HAADF-STEM images do not reveal the presence of Rh NPs
either. However, high magnification images clearly disclose the
Rh NPs with similar size to that of the as-synthesized colloidal
Rh NPs (Figure 1c). In addition, high magnification images also
disclose the existence of Rh NPs on 5Rh/CeO2 (Figure S1c, d).
97
8
1
99
0
-
2.7
3.0
-
99
-
CeO2
0
Reaction conditions: a [Rh] =0.007 mmol, P(CO) = 3 MPa, 50 mg styrene,
120 °C , 12h, 3 ml H2O, 3 ml dioxane. 6 ml dioxane, P(CO) = 1.5 MPa,
b
c
P(H2) = 1.5 MPa. Mole of triphenylphosphine/[Rh] =100, 6 ml dioxane,
P(CO) = 1.5 MPa, P(H2) = 1.5 MPa. d P(CO) = 3 MPa, P(H2) = 0.15 MPa.
e
a
150 mg pure CeO2 support was used with same condition to
to phenylpropyl aldehyde. Selectivity to phenylpropanol. Selectivity to
ethylbenzene was 27%.
.
f Selectivity
g
h
Infrared spectroscopy by using CO adsorption as probe is a
powerful tool to identify the atomic dispersion of a few Pt-group
metals (PGMs)[10] including Pt,[11] Pd[12] and Rh[5, 13]. To further
verify the different dispersion nature of our Rh catalysts, in situ
diffuse reflectance infrared Fourier transform spectroscopy
(DRIFTS) of CO adsorption was performed. As shown in Figure
1b, for Rh1/CeO2 catalyst, two obvious peaks centered at 2081
and 2010 cm-1 are observed which are attributed to the
symmetric and asymmetric vibration of gem-dicarbonyl doublet
CO on positively charged Rh atoms, respectively. A peak
centered at 2052 cm-1 was also observed which corresponds to
the linear CO adsorption on Rh atoms, or to Rh(CO)H/CeO2
species according to a recent report.[14] The absence of bridged-
Hydroformylation of styrene was carried out by using CO
and H2O instead of CO + H2 as reactants. Detailed reaction
conditions and representative results are presented in Table 1.
80% styrene conversion was observed in 12-hour test at 120 oC
and aldehyde products were typically obtained, suggesting a
LWGS was involved since no H2 was originally used.
Quantitative analysis showed a high chemoselectivity of 98% to
phenylpropyl aldehyde and no ethylbenzene was detected,
suggesting hydrogenation of C=C double bond was restrained.
Notably, it was found that the ratio of n-aldehyde to isoaldehyde
is as high as 3. Considering that only when bulky ligands were
used can the high selectivity to linear product in
hydroformylation of styrene be obtained, the high l/b ratio
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obtained in this work without addition of any ligands is quite
surprising.
Different styrene derivatives were explored. As shown in
Table S1. Typically, linear aldehydes were always dominant in
the products of styrene derivative hydroformylation when
coupled with LWGS over Rh1/CeO2 SAC, which strongly implies
that this coupling catalysis route could be a promising solution
for the synthesis of linear product in a certain raw material range.
To deep understand this phenomenon, a series of control
experiments were conducted. Firstly, as shown in Table 1 entry
2-3, hydroformylation of styrene was conducted at traditional
reaction conditions with CO and H2 as reactants. Styrene was
completely converted and phenylpropyl aldehyde was obtained
as well on Rh1/CeO2 catalyst, but with a l/b ratio of only 0.9. The
result is as expected since under traditional conditions
hydroformylation of styrene tends to produce branched aldehyde
rather than the linear one, [3] and suggests that the abnormal l/b
ratio of 3 obtained in this work is more related to the reactants of
CO + H2O rather than to the Rh SAC iteself. A much lower l/b
ratio of 0.4 was obtained when homogenous RhCl(PPh3)3
The stability of the catalyst was also studied. The used
Rh1/CeO2 after 1st run shows the same CO adsorption feature to
that of the fresh one (Figure S4), indicating no sintering of the
Rh single atoms. However, the recycle activity decreased in 2nd
run, Figure S5. Element analysis of the post-reaction sample
reveals a notable Rh losing (from 0.5 wt% to 0.32 wt%),
suggesting the anti-leaching performance of our catalyst needs
to be further improved by tuning the metal-support interaction or
using protectants and so on [19]. This is, however, beyond the
scope of this work which is a proof of concept work that focuses
mainly on demonstrating the feasibility of the new approach.
catalyst was used. This is also as expected and in consistent
17]
with the previous reported results.[2,
We measured the H2
products to be only 0.004-0.007 MPa after reaction. A control
experiment by using CO and a low pressure H2 of 0.15 MPa
(about 20 times of 0.007 MPa) showed that styrene substrate
didn‘t convert at all (entry 4 in table 1), suggesting the produced
low-pressure H2 is insufficient to realize hydroformylation. Based
on this fact we can conclude that a two-step reaction pathway
where CO reacts with H2O to generate H2 and then CO + H2 to
complete the hydroformylation reaction seems not proceed.
Hence, we proposed that in situ H produced from LWGS may
directly participate in the hydroformylation reaction and lead to
this unusual high l/b ratio.
OC
C
H
Rh
H
A
H
CO
Rh
O
O
O
Ce
O
O
H
Ce
OC
D
E
conversion of styrene
Rh
H
100
80
60
40
20
0
4
3
2
1
0
H
the ratio of l/b
CHO
O
H
B
Rh
O
O2C
Ce
Ce
O
OHC
Scheme 1. Proposed reaction route for hydroformylation of styrene by
B
C
A
coupling with LWGS
Figure 2. Conversion and regioselectivity of styrene hydroformylation coupled
with LWGS or secondary alcohol dehydrogenation over Rh1/CeO2. Reaction
conditions: [Rh] =0.007 mmol, P(CO) = 3 MPa, 50 mg styrene, 120 °C, 12 h, 3
ml dioxane; 3 ml H2O for column A, 3 ml isopropanol for column B, 3 ml
benzhydrol for column C.
H-transfer reaction usually follows a Meerwein-Ponndorf-
Verley route (see scheme in Figure S6) where the unsaturated
bond addition takes place through a six membered transition
state[20]. Considering in situ H from LWSG often exists as formic
acid intermediate and/or bidentate formate,[21] we propose a six
membered transition of our catalytic reaction system as
Considering that secondary alcohol dehydrogenation is
18]
another widely reported in situ H donor reaction,[7d,
we
attempted to replace LWGS with secondary alcohol
dehydrogenation to produce in situ and couple with
following: C=C unsaturated bond forms
a six membered
H
transition state with formic acid. According to the Marcovnikov
rule, active H (hydroxyl H) should interact with, and then be
added to, the end of C=C bond. This intermediate structure not
only favors the carbonyl insertion to the end of C=C bond (where
H was added, Scheme 1 A-B) thus forming linear aldehyde, but
also prevents the formation of the stable benzylic Rh-species
induced by the η2 electron donation from the benzene ring
(C⇌DE), and eventually inhibited the selectivity to branched
aldehyde.
hydroformylation reaction. Isopropanol and benzhydrol were
used and the results are presented in Figure 2. Despite the
relatively lower activity, in both cases (B and C) the selectivity to
linear product is much higher than the branched one and the l/b
ratios are similar to that with H2O (A), verifying the unusual
regioselectivity indeed aroused from the in situ H. Besides, the
fact that regioselectivity is uncorrelated with the molecular size
of the hydrogen source may indicate that stereohindrance in this
process barely contributes to the regioselectivity.
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For comparison, heterogeneous Rh NP catalysts (5Rh/CeO2
and NP-Rh/CeO2) and homogenous Rh catalysts of RhCl3 and
RhCl(PPh3)3 were also tested under identical LWGS coupling
conditions. Both heterogeneous catalysts and homogenous
catalysts show 100% chemoselectivity to hydroformylation
product without the presence of ethylbenzene product, Table 1
(entry 1, 5, 6) and S2 (entry 1, 2). Of more significance, similar
high l/b ratio (about 3 folds of that obtained in CO+H2 condition)
to that of Rh1/CeO2 SAC were obtained in all cases, further
confirming the critical role of in situ H rather than the catalysts.
On the other hand, these catalysts also show some different
catalytic performance from that of Rh1/CeO2 SAC. For example,
although both homogeneous catalysts exhibit similar aldehyde
selectivity and a similar high l/b ratio, it is much less active than
Rh1/CeO2 SAC with very low styrene conversion (~8% and 18%)
at identical reaction condition (entry 6 in Table 1). This should be
stemmed from the lower activity of RhCl3 and RhCl(PPh3)3 for
LWGS due to the lack of Rh–CeO2 interfacial sites which was
generally regarded as the reactive site[6b, 22]. To verify this, other
oxide supported Rh catalysts such as 0.5 wt% Rh1/ZnO, 0.5 wt%
Rh1/FeOx and 0.5 wt% Rh1/TiO2 catalysts were also prepared
and tested (Table S2). It shows that except Rh1/ZnO all catalysts
are active for this reaction with high l/b ratio, evidencing the
universality of this strategy. The inactive Rh1/ZnO is as expected
due to the low activity of metal-ZnO interface for LWGS.[23]
homogeneous reaction with a heterogeneous catalysis reaction
which may provide a new avenue for the heterogenization of
homogenous catalysis process.
Experimental Section
Experimental and computational Details are presented in supporting
information.
Acknowledgements
This work was supported by National Natural Science
Foundation of China (21776270, 21972135 and 21606222),
National Key Projects for Fundamental Research and
Development of China (2016YFA0202801), Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDB17020100), DNL Cooperation Fund, CAS (DNL180403)
and LiaoNing Revitalization Talents Program (XLYC1807068).
Keywords: hydroformylation • regioselectivity • in situ H •
styrene • single-atom catalyst
It should be noted that the products obtained on NP
catalysts are mainly corresponding phenylpropanols rather than
aldehydes (entry 5 in table 1). We speculate the different
aldehyde/alcohol selectivity on Rh1/CeO2 and NP-Rh/CeO2 is
caused by their different hydrogenation activity for C=O bond. A
control experiment with benzaldehyde as start materials was
performed under the same reaction condition to prove this. As
shown in Table S3, 32% of benzaldehyde was consumed on
NP-Rh/CeO2 catalyst (entry 2) while Rh1/CeO2 is completely
inactive (entry 1) for this reaction. The products analysis at
different reaction time also reveals that the alcohol was obtained
upon aldehyde reduction, Table S4. In addition, it is worthy of
noting that no C=C hydrogenation was obtained even on Rh NP
catalysts. This is one of the advantages of coupling with LWGS
as ethylbenzene was obtained even on Rh1/CeO2 in traditional
hydroformylation condition (CO+H2), Table 1 entry 2. This
should be due to either the extremely low H2 pressure or the in
situ H that cannot directly hydrogenate C=C bond. A control
experiment, i.e., hydrogenation of styrene with in situ H
generated from secondary alcohol (to avoid the hydroformylation
reaction) was performed. Clearly in situ H is almost inactive for
C=C bond hydrogenation (Table S3 entry 3), implying the latter
is likely the major reason.
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For internal use, please do not delete. Submitted_Manuscript
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10.1002/anie.202000998
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
In aromatic hydroformylation it is
rather challenging to obtain branched
Tianbo Li, Fang Chen, Rui Lang, Hua
Wang, Yang Su, Botao Qiao,* Aiqin
Wang, Tao Zhang*
aldehydes. In this work
a novel
approach to selectively obtain linear
aldehyde in hydroformylation of
Page No. – Page No.
styrene
was
realized
on
Styrene Hydroformylation with In situ
Hydrogen: Regioselectivity Control
by Coupling with Low-temperature
Water-Gas Shift Reaction
heterogeneous Rh catalysts by
coupling with low temperature water
gas shift (LWGS) reaction without
using any ligands. The in situ
hydrogen generated from LWGS
plays a critical role in determining this
regioselectivity.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.