Organic Ligand-Free Hydroformylation with Rh Particles as Catalyst?

Article abstract of DOI:10.1002/cjoc.201900427

An efficient and organic ligand-free heterogeneous catalytic system for hydroformylation of olefins is highly desirable for both academy and industry. In this study, simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in the absence of organic ligand. The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic olefins, affording the desired aldehydes in good yields. Taking the hydroformylation of ethylene as an example, 86% yield of propanal and TOF of 200 h^–1 were obtained, which was superior to the reported homogeneous catalytic systems. In addition, the catalyst could be reused five times without loss of activity under identical reaction conditions, and the Rh leaching was negligible after each cycle.

Full text of DOI:10.1002/cjoc.201900427

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Accepted Article
Title: Organic ligand-free hydroformylation with Rh particles as catalyst
Authors: Shujuan Liu, Xingchao Dai, Hongli Wang, Feng Shi*
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Organic ligand-free hydroformylation with Rh particles as catalyst
Shujuan Liu,a,b Xingchao Dai,a Hongli Wang,a,c Feng Shia*
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No.18, Tianshui
Middle Road, Lanzhou, 730000, China;
b University of Chinese Academy of Sciences, No. 19A, Yuquanlu, Beijing, 100049, China;
c Dalian National Laboratory for Clean Energy, Dalian 116023, China
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion An efficient and organic ligand-free heterogeneous catalytic system for hydroformylation of olefins is
highly desirable for both academy and industry. In this study, simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in
the absence of organic ligand. The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic
olefins, affording the desired aldehydes in good yields. Taking the hydroformylation of ethylene as an example, 86% yield of propanal and TOF of 200 h-1
were obtained, which was superior to the reported homogeneous catalytic systems. In addition, the catalyst could be reused five times without loss of
activity under identical reaction conditions, and the Rh leaching was negligible after each cycle.
either organic polymers or inorganic matrixes modified with
Background and Originality Content
organic phosphine ligands. [47-65] This strategy allows not only their
Hydroformylation is the addition of olefins and synthesis gas
easy separation/reutilization but also the potential enhancement
in the presence of a catalyst for the formation of aldehydes and
of activity and selectivity. However, the use of expensive and
was discovered in early 1938 by Otto Roelen, which represents
sensitive organic phosphine ligand as well as the complicated
one of the largest homogeneously catalyzed reactions in industry
processes for homogeneous catalysts immobilized on support
today and has more than 10 million metric tons of oxo chemicals
limited the further application.
[1-5]
annually.
The aldehyde can be extensively served as key
In the current work, an efficient organic ligand-free
heterogeneous catalytic system for hydroformylation of olefins
was constructed with simple Rh particles as the catalyst. The
catalyst system exhibited excellent catalytic activity in
hydroformylation of olefins, as well as easy separation and
recycle.
intermediates in the synthesis of esters, alcohols, carboxylic acids
and other fine chemicals, which are used for the manufacturing of
plasticizers, surfactants, soaps, and detergents. [6-8]
Over the past years, both industry and academia have
[9]
invested heavily in research related to hydroformylation, and a
number of transition metals, such as Rh, [10-12] Co, [13-15] Ir, [16-19] Ru,
[20-22]
[23-29]
[30-32]
Pt
and Pd
have been used for catalyze olefins
Scheme 1 Organic ligand-free heterogeneous Rh-based catalytic system
for hydroformylation of olefins.
hydroformylation reaction. Much effort has been focused on the
use of Rh complexes as catalysts, due to their better activity and
selectivity in the hydroformylation of olefins than heterogeneous
[6, 33]
ones.
However, the separation and recovery is important
technical problems for the soluble catalysts.
Then, it is highly desirable to develop heterogeneous
Rh-based catalysts. And up to now, Rh supported on many solid
[34-36]
[37]
[38]
supports, such as SiO2,
Cu2O,
ZnO,
carbon materials,
[39-43]
[44]
[45, 46]
TiO2,
and Al2O3,
have been investigated for
heterogeneous olefins hydroformylation. Nevertheless, the
activity and selectivity are usually lower compared with the
corresponding homogeneous catalysts. So it is still extremely
relevant to search for new catalytic systems that effectively
combine the advantages of both heterogeneous and
homogeneous catalysis in the context of widening the range of
applications of hydroformylation in fine chemistry industrial
processes.
One of the main synthetic strategies for achieving these goals
is based on the development of heterogenization of
homogeneous catalysts, which usually tethers metal complexes to
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Report
signals of Rh-22, Rh-60, Rh-325, Rh black and used Rh black
catalysts appeared at 307.4 and 308.5 eV, which indicated the
existence of Rh+ and Rh0 state on the surface of catalysts. However,
the peak intensity of Rh+ in used Rh black catalyst was significantly
lower than other catalysts, which suggested that Rh+ might be
reduced in hydroformylation of olefins. Furthermore, the
morphologies of the catalysts was characterized by SEM and TEM.
SEM images of Rh-22, Rh-60, Rh-325 catalysts (Figure 3(A), 3(B),
3(C) and Figure S1(A), 1(B), 1(C)) displayed a quite rough
morphology, and Rh black and used Rh black catalysts showed a
morphology consisting of nanoparticles (Figure 3(D), 3(E), 3(F),
and Figure S1(D)). The HR-TEM images of Rh black and used Rh
black show a lattice spacing of 0.22 nm, which can be indexed to
the (111) plane of Rh. The N2 adsorption-desorption tests (Figure
S2) showed that the BET surface areas of the catalysts (Table S1)
were in the range of 13.4-62.4 m2/g, and the pore radius were in
the in range of 2.24-13.35 nm, Clearly, the BET surface area and
pore radius of Rh balck, which is 62.4 m2/g and 13.35 nm,
respectively, are larger than other catalysts.
Results and Discussion
Characterization of catalysts
Figure 1 XRD pattern of catalysts. (A) Rh-22 mesh; (B) Rh-60 mesh; (C)
Rh-325 mesh; (D) Rh black. (E) Reused five times Rh black.
The Rh particle catalysts were characterized by XRD, XPS, SEM,
TEM and N2 adsorption-desorption to explore the correlation of
the structure and activity. The XRD patterns of Rh-22, Rh-60,
Rh-325, Rh black and used Rh black catalysts are compared in
Figure 1. The diffraction pattern of Rh particles shows five peaks
at about 41.1°, 47.8°, 69.9°, 84.4° and 89.1°, which can be
ascribed to the (111), (200), (220), (311) and (222) reflections of
Rh (JCPDS no. 870714).
Figure 3 SEM images of (A) Rh-22 mesh; (B) Rh-60 mesh; (C) Rh-325 mesh;
(D) Rh black. TEM images of (E) Rh black; (F) Rh black used five times;
HR-TEM of (G) Rh black; (H) Rh black used five times.
Catalytic performance of catalysts
Then, the catalytic performance of Rh particles catalysts was
tested by the hydroformylation of ethylene as model reaction
(Table 1). Initial hydroformylation experiments were performed at
60 bar syngas (CO/H2 =1:1) with toluene as solvent. Clearly, Rh
black exhibited the best catalytic performance, and the desired
hydroformylation product, propanal, was obtained in 64% yield
(Table 1, entry 1). Lower conversions were observed in the case of
other Rh particles (Rh-22, Rh-60, and Rh-325). Based on the
amount of different Rh particle catalysts used, the TOFs for
propanal formation of Rh-22, Rh-60, Rh-325 and Rh black are 17,
21, 33, and 200 h−1, respectively (Entries 1-4). Thus, the order of
catalytic performance of the different Rh particle catalysts is Rh
black > Rh-325 > Rh-60 > Rh-22. It is clear that the catalytic
performances of the Rh particle are strongly dependent on the
size of Rh particle. In addition, the surface area and pore
distribution of catalyst play important roles in catalytic activity,
surface area, pore volume and average pore radius of Rh black are
large than other catalysts. Therefore, Rh black is the most active
catalyst. As is well known, RhCl3 XH2O, [Rh(COD)Cl]2 and
Figure 2 XPS spectra of catalysts. (A) Rh-22 mesh; (B) Rh-60 mesh; (C)
Rh-325 mesh; (D) Rh black. (E) Reused five times Rh black.
Rh(CO)(acac)2 are classical homogeneous catalysts in
[66, 67]
hydroformylation of olefins.
Much lower TOFs of 39 and 66
h−1were obtained when RhCl3 XH2O and [Rh(COD)Cl]2 were
employed at the same reaction conditions (Entries 5-6).
Further, the electronic properties of Rh particles was
determined by XPS analysis. As shown in Figure 2, The Rh 3d5/2
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Running title
Chin. J. Chem.
Rh(CO)(acac)2 as a catalyst showed a TOF of 161 h−1 (Entry 7), but
it is still lower than that obtained in this work. The by-product of
ethylene hydroformylation was not detected in GC-MS. The
catalytic performance of Rh black has compared with supported
Rh catalysts (Table S2). Surprisingly, the Rh black exhibited better
catalyst activity than supported Rh catalysts except Rh-P-MMCb
containing phosphine ligand.
Scope of the substrates
Next, we examined the substrates scope to test the efficiency
of the Rh black catalyst (Table 2). Both aliphatic (ethylene,
1-propylene, 1-hexene and 1-octene) and aromatic olefins
(styrene, 4-tert-butyl-styrene and α-methyl styrene) served as
starting materials and afforded the desired aldehydes in good
yields and chemical selectivities. As shown in Table 2, aliphatic
olefins such as ethylene, 1-propylene, 1-hexene and 1-octene,
were converted to the corresponding aldehydes with good yields
(74-90%), excellent chemical selectivities (97-99%) and moderate
regioselectivity (n/iso =40:60-47:53) (2a-2d). Similarly, the
hydroformylation reaction of allylbenzene also proceeded well,
affording the corresponding product in 76% yield and 99%
chemical selectiviey with moderate regioselectivity (n/iso = 50:50)
(2e). It should be mentioned that in the case of α-methyl styrene
as the substrate, the desired linear product could be selectively
obtained in 67% yield (2f). In addition, styrene and related
derivatives could be also converted to the corresponding
aldehydes (2g-2h) in 77-93% yields and 95-98% chemical
selectivities. It was noted that substitution at the para-position of
styrene had a significant electronic effect on reactivity. For
examples, styrene bearing electron-donating group at the
para-position led to functionalized aldehyde in 93% yield while
styrene delivered benzenepropanal in 77% yield (2g vs 2h).
Table 1 Screening of the catalyst for the Hydroformylation of ethylene a.
.
a
t
C
+
+
H2
CO
H
C
O
Entry
1
Cat.
n/mmolb
3.89
Yield/ %b
64
TOF/h-1
200
33
Rh black
Rh-325
Rh-60
2c
3c
4c
5c
6
1.93
39
1.24
22
21
Rh-22
1.00
18
17
RhCl3 XH2O
Rh(COD)Cl2
2.28
43
39
1.28
24
66
7
Rh(acac)(CO)2
3.13
55
161
a
Reaction conditions: ethylene (5 mmol), [Rh] (0.01 mmol), CO (3 MPa),
H2 (3 MPa), 100 oC, toluene (2.0 mL), 2 h; The yields of propanal were
b
determined by GC-FID with decane as an internal standard; c 6 h.
Table 2 Substrate scope of olefins.a
Furthermore, the kinetic study on the hydroformylation of
ethylene to propanal was conducted over Rh black catalyst. The
evolution relationships of propanal yield with reaction time at
different temperatures over Rh black catalyst were investigated
(Figures 4(A), Table S3). The data points were used to construct
linear -ln(1-Y) versus time plots, and the observed first-order rate
constants k were obtained from the slopes of the rise lines. These
results reveal that the catalytic conversion of ethylene to propanal
is a pseudo first order reaction process. In addition, the apparent
activation energy barrier (Ea) of the rate-determining step was
calculated according to the Arrhenius equation [k = A e(−Ea/RT)
]
based on the reaction rate constants (k) at different temperatures.
An Arrhenius plot for ethylene hydroformylation in the
temperature interval 87-110 oC was obtained, and the apparent
activation energy for propanal formation was calculated to be
23.1 kJ•mol−1 (Figure 4(B)).
a Reaction conditions: alkenes (5 mmol), [Rh] (0.01 mmol), CO (3 MPa), H2
o
(3 MPa), toluene (2.0 mL), 100 C, 4 h, yields and selectivities of aldehyde
were determined by GC-FID; b alkenes (2 mmol).
Recycling of Rh black catalyst
Figure 4 (A) Effect of temperature on rate of propanal synthesis. Ethylene
(5 mmol), Rh black (0.01 mmol), CO (3 MPa), H2 (3 MPa), toluene (2 mL);
(B) Arrhenius plot for apparent activation energies of the Rh black catalyst.
Finally, the recycling of Rh black catalyst in hydroformylation
of ethylene was tested, as shown in Figure 5 and Table S2. For
each recycling experiment, the catalyst was collected by
centrifugation and sequentially washed with 50 mL ethyl acetate
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First author et al.
Report
and dried in 80 ℃ prior to use. It was found that the Rh black
catalyst can be reused at least 5 cycles with good yield of propanal.
To investigate the leaching of Rh, the reaction solution after each
cycle was determined by ICP-AES in Table S4, and results showed
the Rh leaching is negligible after each cycle.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement (optional)
Financial supports from the NSFC (21633013), the
Cooperation Foundation of Dalian National Laboratory for Clean
Energy of CAS (DNL201901), the ‘Light of West China’ Program,
Fujian Innovation Academy and Key Research Program of Frontier
Sciences of CAS (QYZDJ-SSW-SLH051), are gratefully
acknowledged.
Data availability
The data supporting the findings of this study are available
within the Article and its Supplementary Information files. All
other relevant source data are available from the corresponding
author upon request.
References
Figure 5 Stability test of catalyst: ethylene (43 mmol), Rh black (50 mg), CO
(4.5 MPa), H2 (4.5 MPa), toluene (60 mL), 100 oC, 1 h, yield was
determined by GC-FID with decane as an internal standard.
[1] Neves, A. C. B.; Calvete M. J. F.; Pinho e Melo T. M. V. D.; Pereira M.
M. Immobilized Catalysts for Hydroformylation Reactions: A Versatile
Tool for Aldehyde Synthesis, Eur. J. Org. Chem. 2012,6309-6320.
[2] Van Leeuwen, P. W. N. M.; Claver C. Rhodium catalyzed
hydroformylation, Springer Science
Academic: Dordrecht, The Netherlands, 2002.
[3] Arpe, H. J. Industrial Organic Chemistry, Wiley-VCH: Weinheim,
Germany, 2010.
[4] Breit, B.; Seiche W. Recent advances on chemo-, regio- and
stereoselective hydroformylation, Synthesis 2001, 2001, 1-36.
[5] Gonsalvi, L.; Guerriero A.; Monflier E.; Hapiot F.; Peruzzini M. The
Role of Metals and Ligands in Organic Hydroformylation. In: Taddei
M, Mann A (eds). Hydroformylation for Organic Synthesis, vol. 342,
2013, pp 1-47.
Conclusions
& Business Media, Kluwer
In the present study,
a
simple organic ligand-free
heterogeneous Rh-based catalytic system were developed for the
hydroformylation of olefins. A series of functional aldehydes were
synthesized by simple Rh black catalyst under optimal reaction
conditions, and good yields were generally obtained. Meanwhile,
this catalytic system showed good reusability, and the catalyst
could be reused up to five times without loss of activity.
Experimental
All chemicals, solvent, and Rh particles were obtained
commercially and used as received. The catalysts of Rh-22 mesh,
Rh-60 mesh, Rh-325 mesh and Rh black were purchased from the
company of Alfa Aesar, and the CAS number of Rh particles is
7440166.
[6] Wu, X. F.; Fang X.; Wu L.; Jackstell R.; Neumann H.; Beller M.
Transition-metal-catalyzed carbonylation reactions of olefins and
alkynes:
a personal account, Accounts Chem. Res. 2014, 47,
1041-1053.
[7] Franke, R.; Selent D.; Borner A. Applied hydroformylation, Chem.
Rev. 2012, 112, 5675-5732.
[8] Liu, X. H.; Hu B. S.; Fujimoto K.; Haruta M.; Tokunaga M.
Hydroformylation of olefins by Au/Co3O4 catalysts, Appl. Catal., B
2009, 92, 411-421.
[9] Bohnen, H. W.; Cornils B. Hydroformylation of alkenes: An industrial
view of the status and importance, Adv. Catal. 2002, 47, 1-64.
[10] Tsunoi, S.; Ryu I.; Sonoda N. Remote Carbonylation - the Synthesis
of Delta-Lactones from Saturated Alcohols and Carbon-Monoxide, J.
Am. Chem. Soc. 1994, 116, 5473-5474.
[11] Gil, W.; Trzeciak A. M. N-Heterocyclic carbene–rhodium complexes
as catalysts for hydroformylation and related reactions, Coord.
Chem. Rev. 2011, 255, 473-483.
Rh catalyst (0.01 mmol), olefins (5 mmol), and toluene (2 mL)
were added to a stainless steel autoclave (80 mL) with a magnetic
stir bar. After the autoclave was sealed and purged with CO three
times, the pressure of syngas (CO/H2=1:1) was adjusted to 6 MPa
and the autoclave was put into a preheated reactor, stirring at
100 °C for 4 h. After reaction, the autoclave was cooled to room
temperature and the pressure was carefully released.
Subsequently, the reaction mixture was diluted with 5 mL of ethyl
acetate and the catalyst was removed from the system by
centrifugation and analyzed by gas chromatography (Agilent
7890A GC equipped with a HP-5 capillary column with 5 wt%
phenyl groups and a FID detector). For recycling, the catalyst was
separated by centrifugation, washed with ethyl acetate, dried at
80 °C for 12 h and used directly for the next run.
[12] Fell, B.; Bahrmann H. The hydroformylation of conjugated dienes, v
aliphatic tertiary phosphines and p-substituted phospholanes as
cocatalysts of the rhodium-catalysed hydroformylation of 1,3-dienes,
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
J. Mol. Catal. A: Chem. 1997, 2, 211-218.
Platinum-Phosphine-Tin (II) Halide Systems. Characterization of the
Novel PtI(SnCl3)[(2S, 4S)-2,4-bis (diphenylphosphino) pentane]
Complex, Organometallics 1996, 15, 1345-1350.
[13] Hebrard, F.; Kalck P. Cobalt-catalyzed hydroformylation of alkenes:
generation and recycling of the carbonyl species, and catalytic cycle,
Chem. Rev. 2009, 109, 4272-4282.
[14] Cornils, B.; Herrmann W. A. Applied Homogeneous Catalysis with
Organometallic Compounds: Applications; Volume 2. Developments;
Volume 3. Developments, Wiley-VCH, 2002.
[15] Birbeck, J. M.; Haynes A.; Adams H.; Damoense L.; Otto S. Ligand
Effects on Reactivity of Cobalt Acyl Complexes, ACS Catal. 2012, 2,
2512-2523.
[29] Clarke, M. L. Recent advances in homogeneous catalysis using
platinum complexes, Polyhedron 2001, 20, 151-164.
[30] Konya, D.; Almeida Leñero K. Q.; Drent E. Highly selective halide
anion-promoted palladium-catalyzed hydroformylation of internal
alkenes to linear alcohols, Organometallics 2006, 25, 3166-3174.
[31] Ishii, Y.; Hidai M. Carbonylation reactions catalyzed by
homogeneous Pd–Co bimetallic systems, Catal. Today 2001, 66,
53-61.
[16] Piras, I.; Jennerjahn R.; Jackstell R.; Spannenberg A.; Franke R.;
Beller M.
A
General and Efficient Iridium ‐ Catalyzed
[32] Drent, E.; Mul W.; Budzelaar P. Teaching
a
palladium
Hydroformylation of Olefins, Angew. Chem. Int. Ed. 2011, 50,
280-284.
polymerization catalyst to mono-oxygenate olefins, Comments Inorg.
Chem. 2002, 23, 127-147.
[17] Moreno, M. A.; Haukka M.; Pakkanen T. A. Promoted iridium
complexes as catalysts in hydroformylation of 1-hexene, J. Catal.
2003, 215, 326-331.
[33] Beller, M.; Cornils B.; Frohning C. D.; Kohlpaintner C. W. Progress in
Hydroformylation and Carbonylation, J. Mol. Catal. A: Chem. 1995,
104, 17-85.
[18] Mieczynska, E.; Trzeciak A. M.; Ziolkowski J. J.; Kownacki I.;
Marciniec B. Hydroformylation and related reactions of vinylsilanes
catalyzed by siloxide complexes of rhodium(I) and iridium(I), J. Mol.
Catal. A: Chem. 2005, 237, 246-253.
[34] Marchetti, M.; Paganelli S.; Viel E. Hydroformylation of
functionalized olefins catalyzed by SiO2-tethered rhodium
complexes, J. Mol. Catal. A: Chem. 2004, 222, 143-151.
[35] Borrmann, T.; McFarlane A.; Ritter U.; Johnston J. Rhodium
[19] Fox, D. J.; Duckett S. B.; Flaschenriem C.; Brennessel W. W.;
catalysts build into the structure of a silicate support in the
Schneider J.; Gunay A.; Eisenberg R.
A
model iridium
hydroformylation of alkenes, Open Chemistry 2013, 11, 561-568.
hydroformylation system with the large bite angle ligand xantphos:
reactivity with parahydrogen and implications for hydroformylation
catalysis, Inorg. Chem. 2006, 45, 7197-7209.
[36] Sandee, A. J.; Reek J. N.; Kamer P. C.; van Leeuwen P. W. A
silica-supported,
switchable,
and
recyclable
hydroformylation-hydrogenation catalyst, J. Am. Chem. Soc. 2001,
123, 8468-8476.
[20] Süss-Fink, G.; Schmidt G. F. Selectivity studies on the
hydroformylation of propylene catalysed by the cluster anion
[HRu3(CO)11]−, J. Mol. Catal. 1987, 42, 361-366.
[21] Süss-Fink, G.; Reiner J. The cluster anion [HRu3 (CO) 11]− as catalyst
in hydroformylation, hydrogenation, silacarbonylation and
hydrosilylation reactions of ethylene and propylene, J. Mol. Catal.
1982, 16, 231-242.
[22] Knifton, J. F. Syngas reactions: part XI. The ruthenium
‘melt’catalyzed oxonation of internal olefins, J. Mol. Catal. 1987, 43,
65-77.
[23] van Duren, R.; van der Vlugt J. I.; Kooijman H.; Spek A. L.; Vogt D.
Platinum-catalyzed hydroformylation of terminal and internal
octenes, Dalton Trans. 2007,1053-1059.
[24] van der Vlugt, J. I.; van Duren R.; Batema G. D.; den Heeten R.;
Meetsma A.; Fraanje J.; Goubitz K.; Kamer P. C.; van Leeuwen P. W.;
Vogt D. Platinum complexes of rigid bidentate phosphine ligands in
the hydroformylation of 1-octene, Organometallics 2005, 24,
5377-5382.
[25] Schwager, I.; Knifton J. Homogeneous olefin hydroformylation
catalyzed by ligand stabilized platinum (II)-group IVB metal halide
complexes, J. Catal. 1976, 45, 256-267.
[26] Petöcz, G.; Berente Z.; Kégl T.; Kollár L. Xantphos as cis-and
trans-chelating ligand in square-planar platinum (II) complexes.
Hydroformylation of styrene with platinum–xantphos–tin (II) chloride
system, J. Organomet. Chem. 2004, 689, 1188-1193.
[27] Hsu, C.-Y.; Orchin M. Hydridotrichlorostannatocarbonylbis
(triphenylphosphine) platinum (II), PtH (SnCl3)(CO)(PPh3) 2, as a
selective hydroformylation catalyst, J. Am. Chem. Soc. 1975, 97,
3553-3553.
[37] Jagtap, S. A.; Bhosale M. A.; Sasaki T.; Bhanage B. M. Rh/Cu2O
nanoparticles: Synthesis, characterization and catalytic application as
a heterogeneous catalyst in hydroformylation reaction, Polyhedron
2016, 120, 162-168.
[38] Kontkanen, M.-L.; Tuikka M.; Kinnunen N.; Suvanto S.; Haukka M.
Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts,
Catalysts 2013, 3, 324-337.
[39] Sakagami, H.; Ohta N.; Endo S.; Harada T.; Takahashi N.; Matsuda T.
Location of active sites for 3-pentanone formation during ethene
hydroformylation on Rh/active-carbon catalysts, J. Catal. 1997, 171,
449-456.
[40] Ganga, V. S. R.; Dabbawala A. A.; Munusamy K.; Abdi S. H. R.;
Kureshy R. I.; Khan N.-u. H.; Bajaj H. C. Rhodium complexes
supported on nanoporous activated carbon for selective
hydroformylation of olefins, Catal. Commun. 2016, 84, 21-24.
[41] Li, X.; Zhang Y.; Meng M.; Yang G.; San X.; Takahashi M.; Tsubaki N.
Silicalite-1 membrane encapsulated Rh/activated-carbon catalyst for
hydroformylation of 1-hexene with high selectivity to normal
aldehyde, J. Membr. Sci. 2010, 347, 220-227.
[42] Kainulainen, T. A.; Niemela M. K.; Krause A. O. I. Hydroformylation
of 1-hexene on Rh/C and Co/SiO2 catalysts, J. Mol. Catal. A: Chem.
1997, 122, 39-49.
[43] Li, B. T.; Li X. H.; Asami K.; Fujimoto K. Hydroformylation of
1-hexene over rhodium supported on active carbon catalyst, Chem.
Lett. 2003, 32, 378-379.
[44] Shi, Y.; Hu X.; Chen L.; Lu Y.; Zhu B.; Zhang S.; Huang W. Boron
modified TiO2 nanotubes supported Rh-nanoparticle catalysts for
highly efficient hydroformylation of styrene, New J. Chem. 2017, 41,
6120-6126.
[28] Farkas, E.; Kollár L.; Moret M.; Sironi A. Halogen Exchange in
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Report
[45] Alini, S.; Bottino A.; Capannelli G.; Comite A.; Paganelli S.
Preparation and characterisation of Rh/Al2O3 catalysts and their
application in the adiponitrile partial hydrogenation and styrene
hydroformylation, Appl. Catal. A-Gen. 2005, 292, 105-112.
[46] Navidi, N.; Thybaut J. W.; Marin G. B. Experimental investigation of
ethylene hydroformylation to propanal on Rh and Co based catalysts,
Appl. Catal. A-Gen. 2014, 469, 357-366.
highly efficient heterogeneous catalysts, Chem. Commun. 2014, 50,
11844-11847.
[60] Wang, T.; Wang W.; Lyu Y.; Xiong K.; Li C.; Zhang H.; Zhan Z.; Jiang
Z.; Ding Y. Porous Rh/BINAP polymers as efficient heterogeneous
catalysts for asymmetric hydroformylation of styrene: Enhanced
enantioselectivity realized by flexible chiral nanopockets, Chin. J.
Catal. 2017, 38, 691-698.
[47] Abu-Reziq, R.; Alper H.; Wang D.; Post M. L. Metal supported on
[61] Zhu, H. Supported rhodium and supported aqueous-phase catalyst,
and supported rhodium catalyst modified with water-soluble TPPTS
ligands, Appl. Catal. A-Gen. 2003, 245, 111-117.
[62] Sun, Q.; Dai Z.; Liu X.; Sheng N.; Deng F.; Meng X.; Xiao F. S. Highly
Efficient Heterogeneous Hydroformylation over Rh-Metalated
Porous Organic Polymers: Synergistic Effect of High Ligand
Concentration and Flexible Framework, J. Am. Chem. Soc. 2015, 137,
5204-5209.
[63] Tian, M.; Li H.; Wang L. Highly efficient Rh (I)/tris-H8-binaphthyl
monophosphite catalysts for hydroformylation of dicyclopentadiene
to dialdehydes, Chin. J. Catal. 2018, 39, 1646-1652.
[64] Ren, X.; Zhang L.; Wang Z.; Xia C.; Ding K. Rh-Catalyzed
Hydroformylation of Alkynes to α, β-Unsaturated Aldehydes, J. Mol.
Catal. (China) 2016, 30, 497-504.
dendronized
magnetic
nanoparticles:
highly
selective
hydroformylation catalysts, J. Am. Chem. Soc. 2006, 128, 5279-5282.
[48] Adint, T. T.; Landis C. R. Immobilized bisdiazaphospholane catalysts
for asymmetric hydroformylation, J. Am. Chem. Soc. 2014, 136,
7943-7953.
[49] Arya, P.; Panda G.; Rao N. V.; Alper H.; Bourque S. C.; Manzer L. E.
Solid-phase catalysis: a biomimetic approach toward ligands on
dendritic arms to explore recyclable hydroformylation reactions, J.
Am. Chem. Soc. 2001, 123, 2889-2890.
[50] Bourque, S. C.; Maltais F.; Xiao W. J.; Tardif O.; Alper H.; Arya P.;
Manzer L. E. Hydroformylation reactions with rhodium-complexed
dendrimers on silica, J. Am. Chem. Soc. 1999, 121, 3035-3038.
[51] Gao, H. R.; Angelici R. J. Hydroformylation of 1-octene under
atmospheric pressure catalyzed by rhodium carbonyl thiolate
complexes tethered to silica, Organometallics 1998, 17, 3063-3069.
[52] Huang, L. Effects of supported donor ligands on the activity and
[65] Xiao-Ya, Z.; Cong-Ye Z.; Xue-Li Z.; Hai-Yan F.; Mao-Lin Y.; Rui-Xiang
L.; Hua C. Preparation of Silica-Bonded Phosphine and Its Influence
on 1-Octene Hydroformylation Catalyzed by Rhodium Complex, Acta
Phys. -Chim. Sin. 2015, 31, 738-742.
stability of tethered
rhodium complex catalysts for
hydroformylation, J. Mol. Catal. A: Chem. 2004, 211, 23-33.
[53] Li, C.; Sun K.; Wang W.; Yan L.; Sun X.; Wang Y.; Xiong K.; Zhan Z.;
Jiang Z.; Ding Y. Xantphos doped Rh/POPs-PPh 3 catalyst for highly
selective long-chain olefins hydroformylation: Chemical and DFT
insights into Rh location and the roles of Xantphos and PPh 3, J.
Catal. 2017, 353, 123-132.
[66] Sakai, N.; Mano S.; Nozaki K.; Takaya H. Highly Enantioselective
Hydroformylation
of
Olefins
Catalyzed
by
New
Phosphinephosphite-Rh(I) Complexes, J. Am. Chem. Soc. 1993, 115,
7033-7034.
[67] Chaudhari, R. V.; Bhanage B. M.; Deshpande R. M.; Delmas H.
Enhancement of Interfacial Catalysis in a Biphasic System Using
Catalyst-Binding Ligands, Nature 1995, 373, 501-503.
[54] Li, C.; Yan L.; Lu L.; Xiong K.; Wang W.; Jiang M.; Liu J.; Song X.; Zhan
Z.;
Jiang
Z.;
Ding
Y.
Single
atom
dispersed
(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Rh-biphephos&PPh3@porous organic copolymers: highly efficient
catalysts for continuous fixed-bed hydroformylation of propene,
Green Chem. 2016, 18, 2995-3005.
Manuscript accepted: XXXX, 2019
[55] Nowotny, M.; Maschmeyer T.; Johnson B. F. G.; Lahuerta P.;
Thomas J. M.; Davies J. E. Heterogeneous Dinuclear Rhodium(ii)
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
Hydroformylation
CatalystsÐPerformance
Evaluation
and
Silsesquioxane-Based Chemical Modeling, Angew. Chem. Int. Ed.
2001, 40, 955-958.
[56] Pérez-Cadenas, M.; Lemus-Yegres L. J.; Román-Martínez M. C.;
Salinas-Martínez de Lecea C. Immobilization of a Rh complex derived
from the Wilkinson's catalyst on activated carbon and carbon
nanotubes, Appl. Catal. A-Gen. 2011, 402, 132-138.
[57] Sartipi, S.; Romero M. J. V.; Rozhko E.; Que Z.; Stil H. A.; de With J.;
Kapteijn F.; Gascon J. Dynamic Release-Immobilization of
Homogeneous Rhodium Hydroformylation Catalyst by
a
a
Polyoxometalate
Metal-Organic
Framework
Composite,
ChemCatChem 2015, 7, 3243-3247.
[58] Sun, Q.; Dai Z.; Meng X.; Xiao F.-S. Enhancement of
hydroformylation performance via increasing the phosphine ligand
concentration in porous organic polymer catalysts, Catal. Today
2017, 298, 40-45.
[59] Sun, Q.; Jiang M.; Shen Z.; Jin Y.; Pan S.; Wang L.; Meng X.; Chen W.;
Ding Y.; Li J.; Xiao F. S. Porous organic ligands (POLs) for synthesizing
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Entry for the Table of Contents
Page No.
Organic ligand-free hydroformylation with Rh
particles as catalyst
Shujuan Liu, Feng Shi,* Xingchao Dai, Hongli
Wang
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou
Institute of Chemical Physics, Chinese Academy of Sciences, No.18, Tianshui
Middle Road, Lanzhou, 730000, China;
E-mail: fshi@licp.cas.cn
b University of Chinese Academy of Sciences, No. 19A, Yuquanlu, Beijing,
100049, China
E-mail: fshi@licp.cas.cn
Chin. J. Chem. 2018, template
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
This article is protected by copyright. All rights reserved.