Development of a ruthenium/Phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide

Article abstract of DOI:10.1002/chem.201400358

An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence.

Full text of DOI:10.1002/chem.201400358

DOI: 10.1002/chem.201400358
Full Paper
&
Homogeneous Catalysis
Development of a Ruthenium/Phosphite Catalyst System for
Domino Hydroformylation–Reduction of Olefins with Carbon
Dioxide
[
a]
[a]
[a, b]
[a]
[c, d]
Qiang Liu, Lipeng Wu, Ivana Fleischer,*
Detlef Selent, Robert Franke,
[a]
[a]
Ralf Jackstell, and Matthias Beller*
Abstract: An efficient domino ruthenium-catalyzed reverse
water-gas-shift (RWGS)-hydroformylation-reduction reaction
of olefins to alcohols is reported. Key to success is the use of
specific bulky phosphite ligands and triruthenium dodeca-
carbonyl as the catalyst. Compared to the known rutheni-
um/chloride system, the new catalyst allows for a more effi-
cient hydrohydroxymethylation of terminal and internal ole-
fins with carbon dioxide at lower temperature. Unwanted
hydrogenation of the substrate is prevented. Preliminary
mechanism investigations uncovered the homogeneous
nature of the active catalyst and the influence of the ligand
and additive in individual steps of the reaction sequence.
[
8]
Introduction
the Shell higher olefin process (SHOP) process. Carbonylation
of these alkenes to produce value-added chemicals represents
[9]
The application of carbon dioxide (CO ) as a C1 feedstock for
the basis of today’s chemical industry. Compared to tradition-
al processes using carbon monoxide (toxic and flammable) as
C1 source, the production of higher oxygenates by catalytic
2
chemical synthesis attracts ample interest due to its abun-
[
1]
dance, convenient use, and low toxicity. However, chemical
activation of CO is problematic due to its high thermodynam-
CO fixation with alkene substrates is highly desirable. Illustra-
2
2
ic and kinetic stability. Consequently, the use of CO for the ef-
tive examples include Ni-catalyzed carboxylation of alkenes
2
[10]
ficient construction of CÀC bonds represents a significant chal-
with CO through an oxidative cycloaddition mechanism and
2
[
1d,2]
lenge.
Traditional CÀC bond formation via CO activation is
Fe-, Ni- or Pd-catalyzed hydrocarboxylation of alkenes with
2
[11]
specifically limited to strong nucleophiles, including organo-
lithium, Grignard reagents, and phenolates. Interestingly, in the
CO2.
Unfortunately, the use of sensitive organometallic
reagents in stoichiometric amounts (e.g., Grignard reagents or
[
3]
[4]
past few years, carboxylation reactions of CÀZn, CÀB, CÀ pyrophoric Et Zn) constitutes a major drawback in such
2
[
5]
[6]
[7]
Sn, CÀBr (or Cl), and activated CÀH bonds with CO have
reactions.
2
been studied intensively, since in these reactions functional
groups that are not compatible with Grignard reagents were
tolerated.
In addition, chemical transformation of CO with alkenes can
2
also be achieved through tandem reaction sequences, in
which the reduction of CO to CO is combined with a subse-
2
[12]
Aliphatic alkenes are cheap and produced in bulk scale by
the refinery and petrochemical industry, for example, through
quent carbonylation process. Pioneering work in this area
has been reported by Tominaga and Sasaki, who found that
ruthenium cluster complexes catalyzed the hydroformylation
of alkenes under reverse water-gas-shift-reaction conditions
+
+
[
a] Dr. Q. Liu, L. Wu, Dr. I. Fleischer, Dr. D. Selent, Dr. R. Jackstell,
[13]
Prof. Dr. M. Beller
(RWGS, conversion of CO and H to CO and H O). The ole-
2
2
2
Leibniz-Institut fꢀr Katalyse e.V. an der Universitꢁt Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
E-mail: Matthias.Beller@catalysis.de
fins are converted to higher alcohols in a tandem RWGS-hydro-
formylation-reduction reaction pathway (Scheme 1).
[b] Dr. I. Fleischer
Current address: Institute of Organic Chemistry
University of Regensburg, Universitꢁts Strasse 31
9
3040 Regensburg (Germany)
E-mail: ivana.fleischer@chemie.uni-regensburg.de
[c] Prof. Dr. R. Franke
Evonik Industries AG, Paul-Baumann-Strasse 1, 45772 Marl (Germany)
[d] Prof. Dr. R. Franke
Lehrstuhl fꢀr Theoretische Chemie, 44780 Bochum (Germany)
+
[
] These authors contributed equally to this work.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201400358.
Scheme 1. Ru-catalyzed hydroformylation/reduction of alkenes with carbon
dioxide.
Chem. Eur. J. 2014, 20, 6888 – 6894
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Most recently, Leitner and co-workers reported a Rh-cata-
lyzed hydrocarboxylation of olefins with CO and H through
system gave 33% of the desired alcohol 2a along with 6% al-
dehyde 3a and 22% hydrogenation product 4a. We chose the
ligand-to-metal ratio of 1.1:1 based on our experience with
ruthenium-catalyzed hydroformylation, which is different from
its rhodium-catalyzed equivalent (generally large excess of
2
2
[
14]
a RWGS process. At the same time, our group developed
a Ru-catalyzed alkoxycarbonylation of alkenes with carbon di-
[
15]
oxide and alcohols.
[17k]
Interestingly, although CO -conversion is a major topic in
ligand-to-rhodium ratios are needed).
Unfortunately, the
2
catalysis science, the work of Tominaga et al. has attracted only
minor regards and the efficiency of this promising hydro-
employment of the imidazole-based ligand L1, which was
identified to trigger the formation of an exceptionally active
ruthenium complex for hydroformylation with synthesis gas,
led to a result comparable to the ligand-free system with high
amounts of octene being reduced (Table 1, entries 1–2). A simi-
lar result was obtained with tricyclohexylphosphine L2
(Table 1, entry 3). On the other hand, the less basic triphenyl-
phosphine L3 resulted in higher alcohol yield; however, un-
known high-boiling side products were formed (Table 1,
entry 4). Surprisingly, the employment of monodentate phos-
formylation reaction process with CO is still far from satisfac-
2
[
16]
tory. Based on our continuous interest in the development
[
1e,17]
of alternative systems for olefin carbonylation reactions
[
18]
and sustainable CO reduction methodologies, we decided
2
to explore the ruthenium-catalyzed hydroformylation with
carbon dioxide in more detail and to develop a more efficient
catalyst system. Herein, we report our studies on the develop-
ment of a phosphite-ligand-promoted Ru-catalyzed domino
RWGS/hydroformylation/reduc-
tion of alkenes with CO under
2
milder conditions. Ligand and
[a]
2
Table 1. Hydroformylation of 1-octene with CO : Ligand examination.
additive effects in all the individ-
ual steps are discussed as well.
Results and Discussion
The main drawbacks of the pre-
viously reported catalytic sys-
tems for hydroformylation using
carbon dioxide are the chemose-
lectivity (formation of oxo prod-
ucts versus hydrogenation of the
starting material) and harsh con-
ditions such as high temperature
(
typically 1608C) and pressure
with high catalyst loading
2mol% [Ru (CO) ]). Therefore,
(
3
12
we started our investigations by
performing the model reaction
of 1-octene with CO in the pres-
2
ence of [Ru (CO) ] as the cata-
3
12
[
19]
lyst and LiCl as the additive in
N-methylpyrrolidone (NMP). We
aimed to modify the ruthenium
catalyst with ligands in order to
tune its activity and selectivity.
The main objective was the sup-
pression of alkene hydrogena-
tion and improvement of the re-
action efficiency at milder condi-
tions and lower catalyst loading.
In general, hydroformylations
of 1-octene were performed in
a 25 mL autoclave at 1308C with
[
b]
[b]
Entry Ligand
Yields [%]
n/iso 3a 4a 1a/isomers
Entry Ligand
Yields [%]
2a n/iso 3a 4a 1a/isomers
[c]
[c]
2
a
1
2
3
4
5
6
7
8
9
–
33 65:35
41 49:51
42 48:52
64 51:49
71 54:46
76 51:49
63 56:44
6
0
3
3
2
1
2
22 10
9
L8
72 56:44
55 56:44
36 56:44
6
5
4
2
2
7
4
3
6
7
12
18
3
4
[
d]
L1
L2
L3
L4
L5
L6
L7
L8
L9
27
34
15
19
15
13
0
0
2
3
3
1
2
3
4
10
11
12
13
14
15
16
17
18
L9
L10
L11
L12
L13
L14
L15
L16
L17
49 12
10 42
2
-
45 53:47
59 51:49
34 56:44
23
20
6
7
49 12
61 28
24 51
76 53:47 1.5 12
3
–
72 56:44
55 56:44
6
5
12
18
11 64:36
67 57:43
3
0 bar CO2 and 30 bar H . The
10
16
7
2
catalyst system consisted of
Ru (CO) ], LiCl, and selected li-
[
a] A 25 mL Parr-autoclave was filled with [Ru
3
(CO)12] (16 mg, 25 mmol), ligand (82 mmol), LiCl (53 mg, 1.2 mmol)
and 30 bar H and heated
[
and 1-octene (0.78 mL, 0.56 g, 5.0 mmol) in NMP (6 mL), pressurized with 30 bar CO
to 1308C for 24 h. [b] Determined by GC with isooctane as internal standard. [c] Mixture of 1-, E- and Z-2-, E-
and Z-3- and E- and Z-4-octene. [d] 48 h.
2
2
3
12
gands in a ratio of 0.5:25:1.65.
The reported P-ligand-free
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phite L4 led to a significant improvement of chemoselectivity
Table 1, entry 5). The desired C9-alcohols were obtained in
1% yield and only 19% of the hydrogenated product was de-
tected. Phosphites are widely used ligands in homogeneous
(
7
[
20]
catalysis, and stand out due to their low susceptibility to oxi-
[
21]
dation and simple synthesis. Owing to their electronic prop-
erties, they are employed in rhodium-catalyzed industrial hy-
[
22]
droformylations. Often, bulky aryl substituents are attached
to the phosphorous center to prevent degradation reactions,
[23]
such as hydrolysis, alcoholysis, or Arbusov rearrangement.
Thus, we investigated the influence of different structural pa-
rameters of the phosphites on the outcome of hydroformyla-
tion reactions with carbon dioxide. Starting from industrially
available 3,3’-di-tert-butyl-5,5’-dimethoxybiphenyl-2,2’-diol and
various phenol derivatives, ligands L5–9 were synthesized and
tested in the hydroformylation/reduction of 1-octene under re-
verse water-gas-shift conditions. Interestingly, the ortho-sub-
stituents on the phenol ring had a significant influence on the
reaction outcome. Both ligands L5 based on methyl-substitut-
ed phenol and L7 (phenol) provided the alcohol 2a in good
yield (76%, Table 1, entries 6 and 8). Two methyl groups in
ligand L6 led to diminished activity and formation of side
products (Table 1, entry 7), while the presence of tert-butyl
group resulted in slower hydrogenation of the aldehyde 3a to
the desired product (Table 1, entry 9). The ligand L9 bearing
a methoxy group gave only moderate result (Table 1, entry 10).
Furthermore, hexafluoroprop-2-yl substituted ligand L10 exhib-
ited strong alkene hydrogenation activity (Table 1, entry 11).
Only negligible amounts of oxo products were detected with
the bidentate phosphite L11 (Table 1, entry 12). Moreover, the
commercially available phosphite L12 bearing bulky nonbridg-
ed aryl groups provided only 45% yield of alcohols (Table 1,
entry 13). Substitution of one of the aryl groups by benzyl led
to the more effective ligand L13 with 55% yield, while alkyl-
substituted phosphites L14, 15 displayed considerably lower
hydroformylation activity (Table 1, entries 14–16). 1-Naphthol-
based ligand L16 led to low reactivity (Table 1, entry 17), while
bulky ligand L17 performed well and furnished the desired C9-
alcohols in 67% yield together with 7% of the corresponding
aldehydes (Table 1, entry 18).
2
Figure 1. Hydroformylation of 1-octene 1a with CO : Influence of the partial
pressures of carbon dioxide and hydrogen.
Figure 2. Hydroformylation of 1-octene 1a with CO : Reaction progress.
2
Reaction shown in Figure 1.
and 3a) versus concentration of alkenes (1a and isomers) and
octane (4a). Time 0 h represents the moment when the reac-
tion temperature was reached. The starting material 1-octene
1a isomerized completely to a mixture of internal olefins
during the heating phase mostly to 2- and 3-octenes. At the
early stage of the reaction (1 hour), nonanal and the regioiso-
meric C9-aldehydes are the main products of the reaction.
Later, the alcohols predominate and the amount of aldehydes
drops slowly.
Next, the performance of one of the most successful ligands
(
L5) was investigated in more detail. As shown in Figure 1, the
influence of the pressure was studied and the partial pressure
of the gas components was varied. Noteworthy, both 2:1 and
1
:2 CO /H ratios led to somewhat lower yields of oxo products
2 2
compared to a 1:1 ratio. Interestingly, higher partial carbon di-
oxide pressure resulted in an increased amount of alkane side
products, probably due to a slower RWGS reaction, which
clearly requires higher hydrogen pressure. On the other hand,
higher hydrogen pressure also increased the hydrogenation
rate. The reduction of the total pressure to 40 bar resulted in
a slower overall reaction, while higher pressure (80 bar) did not
improve the yield of alcohols significantly.
To test the stability of the ruthenium catalyst, after 24 h of
reaction, cooling to room temperature, and releasing the pres-
sure, a new portion of substrate and gases was added and the
reaction mixture was heated back to 1308C (Figure 3). Notably,
the reaction took place, demonstrating the stability of the cat-
alyst system, albeit at a slower rate. After additional 40 h, C9-
oxo products were obtained in 84% overall yield (80% 2a, 4%
3a).
Then, we investigated the dependence of the composition
of the reaction mixture on reaction time under standard condi-
tions (1308C, 30 bar CO , 30 bar H , ligand L5). Figure 2 depicts
Encouraged by the above result, we further tested the cata-
lyst activity using 0.05 mol% Ru loading (Scheme 2, Eq. (1)). To
our delight, the desired product 2a is still obtained in 30%
2
2
the changes in the concentrations of the oxo-products (2a
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2
Figure 3. Hydroformylation of 1-octene 1a with CO : Stability test. Reaction
shown in Figure 1.
Scheme 3. Identification of the nature of active catalyst.
water-gas-shift reaction, the hydroformylation/reduction se-
quence, the reduction of the aldehyde and also the hydroge-
nation of the alkene were investigated independently under
similar conditions as the parent overall reaction sequence.
First, the reverse water-gas-shift reaction was performed with
30 bar CO2 (corresponds to 31 mmol) and 30 bar H2 in the
presence of 25 mmol ruthenium dodecacarbonyl (Figure 4a).
The amount of formed carbon monoxide was determined by
gas chromatography. It is shown that L5 has no influence on
the reaction outcome while lithium chloride is essential for this
Scheme 2. Hydroformylation of 1-octene 1a with CO
2
: Activity test.
reaction step. Notably, even at 1108C CO was converted to
2
carbon monoxide, albeit with lower turnover number.
Subsequently, the hydroformylation/reduction sequence was
carried out with carbon monoxide (Figure 4b). Only 5 bar of
CO was applied to mimic its low concentration under the
RWGS conditions. In contrary to the first step, a strong effect
of the ligand L5 is observed and C9-alcohols are obtained as
main products with L5, whereas in the absence of the ligand,
the production of octane predominated. Hence, it is proposed
that the phosphite ligand promotes the carbonylation step. Tri-
phenylphosphine was used as a reference ligand since it also
gave relatively good result for this transformation and is a very
commonly used ligand in homogeneous catalysis (Table 1,
entry 4). Interestingly, its performance was worse than that of
L5. Employment of an excess of ligand inhibited the hydrofor-
mylation/reduction process. The yield of oxo-products (2a and
3a) was also reduced when the reaction was performed with-
out lithium chloride. The hydroformylation step is also likely af-
fected by lithium chloride.
yield. Here, the corresponding turnover number (TON) is up to
00 based on Ru, which is at least one order of magnitude
higher than all the previously reported results (TON=10–
2
[
13]
1
5). Notably, sufficient catalyst activity is observed even at
15 8C leading to a 55% yield of 2a and 13% yield of 3a after
4 h. This example represents the lowest temperature for any
1
2
known carbonylation reactions of olefins with CO . Obviously,
2
this demonstrates that the reverse water-gas-shift reaction can
be performed at such a low temperature and affirms the po-
tential of this reaction. In comparison, the ligand-free catalyst
is much less efficient and only 22% of the alcohol 2a and 11%
3
a were formed (Scheme 2, Eq. (2)).
To understand the nature of the active catalyst (homogene-
0
ous or heterogeneous) in this process, standard Hg poisoning
tests and control reactions using 1-octene, carbon dioxide, and
hydrogen were performed with self-made ruthenium nanopar-
ticles stabilized by ionic liquids as well as a commercially avail-
able Ru/C catalyst (Scheme 3). Adding mercury to a standard
carbonylation reaction did not change the yield of 2a, which
supports the homogeneous nature of the catalyst. In agree-
ment with this observation, the above-mentioned heterogene-
ous Ru catalysts showed no activity at all for this transforma-
tion.
In addition, the hydrogenation activity dropped dramatically
in the reduction of the aldehyde to alcohol in the absence of
lithium chloride and with excess ligand, for which an aldol re-
action took place as well (Figure 4c). We propose that LiCl also
acts as a Lewis acid catalyst to facilitate the reduction of alde-
hyde intermediate. On the other hand, the presence of the
ligand (L/[Ru] 1:1) did not significantly influence the reaction
outcome. Finally, only small effects were observed in the re-
duction of the alkene to alkane, which was almost complete
under the studied conditions (Figure 4d). Moreover, during the
In order to gain more insights into the reaction mechanism,
the influence of the L5 and LiCl on the separate steps of the
reaction sequence was studied (Figure 4). Thus, the reverse
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Figure 4. Influences of ligand and LiCl on the individual reaction steps: a) reverse water-gas-shift reaction; b) hydroformylation/reduction with CO; c) reduc-
tion of the aldehyde; d) reduction of the alkene.
overall reaction process, CO and aldehyde were always detect-
able. This illustrates that the hydrogenation of the aldehyde
and the hydroformylation of internal olefins are slow com-
pared to the initial reverse water-gas-shift step.
along with the appearance of octane 4a. In line with this ob-
servation, the reaction of internal alkenes, such as 2-octene
1b, gave almost the same yield and selectivity compared to 1-
octene 1a (Table 2, entries 1–2). 3,3-Dimethylbut-1-ene gave
the corresponding terminal alcohol in 45% yield highly regio-
selectively (Table 2, entry 4). In the case of the industrially inter-
esting reaction of ethylene 1e, 1-propanol was obtained in
51% yield without further optimization. Applying cyclic olefins,
for example cis-cyclooctene 1 f, cyclohexene 1g as well as cy-
clopentene 1h, led to alcohol products in 68–90% yields (en-
Encouraged by these results, we studied the generality of
the hydroformylation/reduction with different alkenes, carbon
dioxide, and hydrogen (Table 2). Apart from 1-octene 1a, the
reaction with lower terminal aliphatic alkene 1c proceeded
smoothly to afford the alcohols in high yield (Table 2, entry 3).
In these examples, a mixture of the branched and linear alco-
hols was formed. The kinetic profile of the benchmark reaction
[13b]
tries 5–8). In contrast to a literature report,
in which 1,1-di-
(
Figure 2) revealed fast conversion of 1a into internal alkene
phenylethylene was a difficult substrate (9% yield of the de-
sired product), our catalyst system was able to convert this
isomers. Then, the alcohols 2a were produced at a lower rate
Chem. Eur. J. 2014, 20, 6888 – 6894
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(
(
82.5 mmol, 1.65 mol%), LiCl (53.0 mg, 1.25 mmol, 25 mol%), alkene
5.0 mmol) and NMP (6 mL) under argon atmosphere. The auto-
[
a]
2
Table 2. Hydroformylation of different alkenes with CO .
clave was then pressurized with CO (30 bar) and H (30 bar) and
2
2
the reaction was carried out at 1308C for 24 h. Then, the autoclave
was cooled to room temperature and depressurized. The reaction
solution was diluted with acetone and analyzed by gas chromatog-
raphy using isooctane as internal standard.
[
b]
Entry
Yield [%] (n/iso)
1
2
3
1-octene
2-octene
1-pentene
1a
1b
1c
76 (49:51)
75 (49:51)
88 (57:43)
Acknowledgements
4
5
1d
1e
45 (>99:1)
We are grateful to the Bundesministerium fꢁr Bildung und For-
schung (the German Federal Ministry of Education and Re-
search) for financial support under the Valery project (No.
O1RC1011C), Alexander von Humboldt Foundation (grant for
Q.L), Chinese Scholarship council (grant for L.W.), Fonds der
chemischen Industrie (Liebig Fellowship for I.F.) and Evonik In-
dustries AG. We thank Dr. Christine Fischer, Susann Buchholz,
Susanne Schareina, Andreas Koch and Dr. Wolfgang Baumann
for their technical and analytical support.
51
6
1 f
80
7
8
9
1g
1h
1i
90
68
48
[
(
a] 25 mL Parr-autoclave was filled with [Ru
82 mmol), LiCl (53 mg, 1.2 mmol) and alkene (5.0 mmol) in NMP (6 mL),
and 30 bar H and heated to 1308C for 24 h.
b] Determined by GC with isooctane as internal standard.
3
(CO)12] (16 mg, 25 mmol), L5
Keywords: alkenes · carbon dioxide · hydroformylation ·
phosphite · ruthenium
pressurized with 30 bar CO
[
2
2
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12
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Published online on May 8, 2014
Chem. Eur. J. 2014, 20, 6888 – 6894
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