Polyether phosphite for hydroformylation of higher olefins in non-aqueous system and catalyst recovery

Article abstract of DOI:10.1016/S0022-328X(02)01378-5

A new rhodium catalyst recyling system for non-aqueous hydroformylation of 1-decene is described using a polyether phosphite, OPGPP with a polyether chain of over 19 ethylene glycol units. The corresponding rhodium complexes formed in situ are active for non-aqueous hydroformylation of 1-decene. The catalysts precipitated from the reaction mixture on cooling to room temperature or lower and were reused up to six times without obvious decrease in activity. P loss in the seventh reaction run was detected to be 0.92%. Complex OPGPP/Ru₃(CO)₃ formed in situ has also been proved to be a moderate catalyst for the non-aqueous hydroformylation of 1-decene. The catalysts retained considerable activity up to 87.1% after four successive reaction runs.

Full text of DOI:10.1016/S0022-328X(02)01378-5

Journal of Organometallic Chemistry 654 (2002) 83Á90
/
www.elsevier.com/locate/jorganchem
Polyether phosphite for hydroformylation of higher olefins in non-
aqueous system and catalyst recovery
Xiaozhong Liu a,b,*, Hongmei Li b, Yanhua Wang a, Zilin Jin a
a State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China
b Institute of Organic Chemistry, Department of Chemistry, Peking University, Beijing 100871, China
Received 20 August 2001; received in revised form 27 February 2002
Abstract
A new rhodium catalyst recycling system for non-aqueous hydroformylation of 1-decene is described using a polyether phosphite,
OPGPP with a polyether chain of over 19 ethylene glycol units. The corresponding rhodium complexes formed in situ are active for
non-aqueous hydroformylation of 1-decene. The catalysts precipitated from the reaction mixture on cooling to room temperature or
lower and were reused up to six times without obvious decrease in activity. P loss in the seventh reaction run was detected to be
0.92%. Complex OPGPP/Ru3(CO)3 formed in situ has also been proved to be a moderate catalyst for the non-aqueous
hydroformylation of 1-decene. The catalysts retained considerable activity up to 87.1% after four successive reaction runs. # 2002
Elsevier Science B.V. All rights reserved.
Keywords: Phosphite; Rhodium; Hydroformylation; Catalyst separation
1. Introduction
solvents, especially water, methanol etc., has also to be
considered in practical industry.
Considerable attention has been paid to aqueous/
organic biphasic catalysis in the benign, economic
chemical process, which has been regarded as a royal
road to surpass catalyst-product separation and catalyst
Another approach to facilitate catalyst-product se-
paration has long been attached for the catalyst to a
polymeric, organic (e.g. polystyrene, dendrimers) or
inorganic (e.g. polysiloxanes) resin [8Á10]. Nevertheless,
/
recycling [1Á3]. However, limitations of water as solvent
/
activity decrease suffering from diffusion of catalyst in
solvent was often encountered and catalyst leaching
remained a problem for industrial application. Recently,
transition-metal catalysts with soluble supports were
highlighted in literature due to the characteristic ad-
vantage of one-phase catalysis and easy separation of
the catalysts from the mixture by various procedures
were inevitably confined such as in a system with water
sensitive catalyst or substrates, at the same time,
existence of water as solvent decreases regioselectivity
for asymmetric catalysis compared to non-aqueous
homogeneous catalysis. New reaction mediums avoiding
water as solvent, such as perfluorinated hydrocarbons
and ionized solvents have been new focal points [4Á7].
/
[11Á13]. Polyethylene glycol (PEG) derivatives have
/
However, it is questionable whether the recently an-
nounced FBS and NAILs would achieve a breakthrough
in larger scale industry, because of the toxicity of the
perfluorinated hydrocarbons and the corresponding
perfluorinated phosphines as ligands and requirement
of strict purity for the ionized solvents, respectively. The
much higher price of these special solvents than normal
long found their application in combinational synthesis
such as synthesis and purification of peptide and zymes.
Previously we reported some polyether-derived triphe-
nylphosphine ligands and their application in aqueous/
organic biphasic hydroformylation of higher olefins
[14Á17]. It has been recently observed that these
/
polyether phosphines are slightly soluble in some apolar
solvents such as toluene and heptane at room tempera-
ture, providing a good approach to meet simple catalyst
separation and recovery after reaction.
* Corresponding authors. Fax: ꢀ
/
86-10-6275-1708.
E-mail address: xzchem@hotmail.com (X. Liu).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 3 7 8 - 5

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X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á90
/
The use of phosphite in the rhodium catalyzed
OPGPPs with different glycol units possess different
solubility in ambient toluene, heptane and other sol-
vents. The results are summarized in Table 1.
hydroformylation has received much attention because
of its great improvement in activity compared to the
generally employed triphenyl phosphine (TPP), espe-
cially obvious for the long linear olefins and less active
As is indicated in Table 1, OPGPPs derived from
PEG-R dissolve in polar solvents such as CH2Cl2 and
THF at room temperature. Lower OPGPP with 600
weight has considerable solubility in toluene, while it is
insoluble in heptane at room temperature. With increas-
ing weight of OPGPP, it has decreasing solubility in
apolar solvents such as heptane. When n is equal to 58,
OPGPP has a slight solubility of 0.3250 mg P in 100 ml
heptane, indicating very slight (0.045%) loss of phos-
phite in solvent. From the viewpoint of catalyst recov-
ery, higher OPGPP and apolar solvents such as heptane
are preferred for non-aqueous homogeneous catalysis.
internal olefins [18Á20]. Separation of catalyst from
/
products in industry is mainly done through distillation,
which requires strict thermal conditions and inevitably
increases the byproducts. The higher temperature re-
quired for separation of hydroformylation products of
higher olefin causes worse decomposition of the mod-
ified complexes and some phosphites, eventually indu-
cing worse leaching of catalyst.
We previously reported a novel polyether phosphite
(OPGPP) to facilitate aqueous two-phase hydroformy-
lation of water-immiscible higher olefins and styrene,
but there was a considerable loss in activity after four
successive reaction runs owing to the hydrolysis of the
phosphite in water [21,22]. In this paper, we suggest
polyether phosphite OPGPP for the hydroformylation
of higher olefins in the absence of water. It was observed
that the catalyst precipitated quantitatively from the
reaction mixture on cooling to room temperature or
lower temperature. The catalyst was easily recovered by
simple decantation after reaction.
2.1.2. Solubility of OPGPP at different temperature
OPGPPs exist as a liquid at temperatures above
40 8C, which means that two liquid phases coexist
with OPGPPs as one of them, since only a very small
amount of OPGPPs dissolve in some solvents even at
higher temperature. From Fig. 1, no more than 3.33% of
OPGPP (nꢁ58) dissolves in heptane at 90 8C at which
/
phosphite for hydroformylation of higher olefins is
usually employed. The sudden increase in phosphorus
solubility around 70 8C may be ascribed to the existence
of critical solubility temperature (CST) [25,26] in this
system. This work is in progress.
2. Results and discussion
2.1. Solubility of phosphines in organic solvents
2.2. OPGPP/Rh catalyzed hydroformylation of higher
olefins
2.1.1. Solubility of polyether phosphines in solvents at
room temperature
Previously we reported the hydrolysis of OPGPP in
aqueous two-phase catalysis, in which considerable loss
of catalyst was observed in the recycling runs. This may
be avoided by using non-aqueous catalytic system.
Solubility of OPGPP from Table 1 demonstrates that
the least catalyst loss in apolar solvents such as heptane
occurs when higher OPGPPs are employed as ligands. In
this work, OPGPP with 58 glycol units was taken as
ligand for non-aqueous hydroformylation of higher
olefins. To compare the results properly, data obtained
at the same reaction time are presented. After reaction,
the catalysts formed in situ are rose viscous fluid or wax
at lower temperature or room temperature.
As was demonstrated in literature, poly(ethylene
glycols) (PEGs) and their derivatives with weight of
1500Á6800 can be quantitatively precipitated from
/
benzene, acetone, methanol, or methylene chloride by
addition of heptane, ethyl ether, or sometimes by
cooling to low temperature [23,24]. These properties
combined with their easy functionalization offer a
possibility of designing various soluble but recoverable
materials such as catalysts and synthetic intermediates
[23,24]. At room temperature, the PEGs in the weight
range from 1500 to 6800 have only a slight solubility of
less than 0.1% in heptane, implying that catalyst with
them as support will be better recovered after the
reaction. Comparing the structure and weight of
OPGPP with that of the corresponding PEGs, OPGPPs
do not suffer from changes in physical characters such
as solubility in solvents. In view of recovery of catalysts
with PEG as support, longer PEGs benefit in facilitating
catalyst separation. In addition, PEGs precipitate in
cooled toluene or ethanol while they dissolve in hot
solvents. This provides an approach to prepare ther-
merseparable catalyst in homogeneous catalysis.
2.2.1. Effect of reaction temperature
It is known that an increasing reaction temperature
induced an enhancement in reaction rate. 80% conver-
sion of 1-decene was obtained at 70 8C, more than two
times that obtained at 60 8C (see Table 2). TOF reaches
up to 250 hꢂ1 at 90 8C. In general, less than 2.0 n/iso
aldehyde ratio was achieved with a 42Á
aldehyde at 60Á100 8C. No hydrogenation product of
aldehyde was detected in the reaction mixtures.
/
60% of linear
/

X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á
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85
Table 1
Solubility of OPGPP in heptane and toluene at ambient temperature
a
b
c
Ligand solubility in solvent (%)
Polyether chain length of OPGPP (n)
Solvent
Temperature (8C) Solubility (mg P mlꢂ1 solvent)
12
12
19
19
34
58
58
58
58
Heptane 16
Toluene 16
Heptane 16
Toluene 16
Heptane 16
Heptane 16
Toluene 16
CH2Cl2 16
154.5000
/
42.4100
14.72
Fully soluble
5.55
/
9.0375
Largely soluble
Partly soluble
0.045
0.3250
171.7625
27.35
Fully soluble
Fully soluble
/
/
THF
16
a
b
2.054ꢃ
/
10ꢂ4 mol OPGPP/6.0 ml organic solvent.
Ligand solubility: P content in solvent/total P addition.
c
the color of the reaction mixture with toluene, 1,4-
dioxane, anisol, turned out to be somewhat yellow,
indicating obvious loss of catalyst in the reaction
mixture. In comparison, reaction mixture is colorless
in heptane. 4 h were needed to reach up to 98% or so
conversion in heptane, while 3 h was enough for toluene,
1,4-dioxane and anisol. This difference may be the result
of different solubility of phosphines in various solvents
under the reaction conditions. It can be observed that
OPGPP dissolves fully in toluene and anisol at tem-
peratures above 50 8C, while just quantitative OPGPP
dissolves in heptane even at 80 8C (Fig. 1). Interestingly,
it was observed that OPGPP dissolves fully in heptane
with accumulation of some quantitative amount of
aldehydes. So we assume that the reaction takes place
in toluene in homogeneous catalysis. However, with
heptane as solvent, homogeneous catalysis and hetero-
geneous catalysis take place in competition in the early
stage of the reaction and when product aldehydes
accumulate up to some amount, the reaction becomes
homogeneous.
Fig. 1. Solubility of OPGPP (nꢁ58) at different temperatures.
/
2.2.2. Effect of solvents
From Table 3, use of toluene, 1,4-dioxane, anisol, and
heptane as solvents promotes almost full conversion of
substrate after 4 h. Nevertheless, it was observed that
Table 2
Effect of temperature on the reaction
a
Temperature (8C)
Conversion (%)
Aldehyde yield (%)
n-Undecanal content (%)
Aldehyde n/iso
60
70
31.4
80.0
95.1
99.4
99.7
25.2
77.7
94.2
97.6
95.3
60.0
56.7
51.0
48.5
42.0
1.50
1.31
1.04
0.94
0.72
80
90
100
Reaction conditions: 1-decene 2.0 ml, heptane 4.0 ml, internal standard 0.3 ml, Rh(acac)(CO)2 1.058ꢃ
P(H2)ꢁ1:1, Syngas pressure 5.0 MPa, reaction time 4 h.
n-Undecanal contentꢁn-undecanal/total aldehyde.
/
10ꢂ5 mol, OPGPP/Rhꢁ
13, P(CO)/
/
/
a
/

86
X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á90
/
Table 3
Hydroformylation in different organic solvents
Solvent
Reaction time (h)
Conversion (%)
Aldehyde yield (%)
Aldehyde n/i
Toluene
3
3
3
3
4
3
4
97.3
98.7
75.0
98.0
98.7
86.4
99.4
95.6
97.2
74.3
97.2
95.4
86.4
97.6
0.92
0.93
0.98
0.93
0.92
1.21
0.94
1,4-Dioxane
n-Butyl ether
Anisole
Cyclohexane
Heptane
Heptane
Reaction conditions: 1-decene 2.0 ml, solvent 4.0 ml, internal standard 0.3 ml, Rh(acac)(CO)2 1.058ꢃ
/
10ꢂ5 mol, OPGPP/Rhꢁ
/
13, P(CO)/P(H2)ꢁ
/
1:1, 90 8C, Syngas pressure 5.0 MPa.
2.2.3. Effect of phosphine/rhodium ratio
E, and H ligands and their rhodium complexes pre-
cipitated as a separate phase from heptane after reaction
at room temperature. Catalyst separation could be
reached by simple decantation.
Table 4 summarized the results from varying the
phosphine/Rh ratio and addition of TPP. All results
remained similar as the phosphite/Rh ratio was in the
range of 13Á30. Lower phosphite/Rh ratio below 13
/
decreased the conversion and caused a clear loss of
catalyst evidenced by the color of the mixture. Colorless
mixture was obtained with a phosphite/Rh ratio of more
than 13. Addition of TPP caused a slight increase in n/
iso ratio of aldehydes from 0.94 to 2.3. Meanwhile,
addition of TPP to the reaction system induced a slightly
yellow solution.
2.4. Catalyst recycling
The separated catalyst by simple decantation was
employed in the successive reaction runs. Results of the
catalyst recycling were shown in Table 6. Loss of
phosphite in organic phase was determined by ICP
technique.
After reaction, the catalyst precipitated as rose
viscous wax or mash from the reaction mixture on
cooling to room temperature. The separated catalyst
was reused up to six times without apparent decrease in
activity. Compared with phosphite/Rh catalysts usually
separated by distillation in industrial practice, the
polyether phosphite modified catalyst possesses an
obvious advantage in separation from the product after
reaction. Analysis of phosphite in product phase in-
dicated that P loss in reaction mixture after first reaction
and second reaction was 7.8 and 7.2% of the original
total P, respectively. In more reaction runs, loss of P in
the reaction mixture decreased. Loss of P in the seventh
reaction run was detected to be only 0.92% of the
original total P. This gradual decreasing loss of P in
organic phase may be induced by the weight distribution
2.3. Comparison of some polyether phosphine/Rh
catalyzed non-aqueous hydroformylation of 1-decene
We also studied the effects of some different polyether
phosphines on the hydroformylation and catalyst se-
paration. The comparison was summarized in Table 5.
From Table 5, phosphine A-H/Rh catalysts show
considerable activity for the non-aqueous hydroformy-
lation of 1-decene with heptane as solvent, while
OPGPP/Rh catalyzed the reaction with the highest
conversion. Therefore, a conversion of 99.4% 1-decene
and yield of 97.6% aldehydes were obtained in 4 h with
OPGPP (nꢁ
Rh(acac)(CO)2 with OPGPP (n equal to 58) (Pꢁ
MPa, Tꢁ90.0 8C). In view of catalyst separation, A, B,
/58)/Rh as catalyst formed in situ from
/
5.0
/
Table 4
Effect of OPGPP/Rh (mol) ratio and triphenylphosphine on the reaction
OPGPP/Rh (mol)
PPh3/Rh
1-Decene conversion (%)
Aldehyde yield (%)
Aldehyde n/iso
3
7
75.3
90.0
99.4
99.7
99.7
54.3
94.0
95.5
93.8
73.5
88.3
97.6
98.5
98.9
53.2
93.1
94.6
93.8
0.94
0.96
0.94
0.98
0.99
0.98
1.3
13
20
30
3
3
4
13
13
13
13
4.
1.8
2.3
Reaction conditions: 1-decene 2.0 ml, heptane 4.0 ml, internal standard 0.3 ml, Rh(acac)(CO)2 1.058ꢃ
/
10ꢂ5 mol, P(CO)/P(H2)ꢁ
1:1, 90 8C,
/
Syngas pressure 5.0 MPa, reaction time 4 h.

X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á
/90
87
Table 5
Hydroformylation catalyzed by polyether phosphines/Rh catalyst in the absence of water
TRPTC ligand
Conversion (%)
Aldehyde yield (%)
Catalyst separation (by precipitation)
A
B
56.7
31.3
74.3
67.3
78.6
99.7
99.5
99.4
56.3
31.3
73.1
63.2
78.6
97.1
96.9
97.6
Clear
Clear
C
D
E
Turbid
Turbid
Clear
F
Turbid
Turbid
Clear
G
H
Reaction conditions: 1-decene 2.0 ml, heptane 4.0 ml, internal standard 0.3 ml, Rh(acac)(CO)2 1.058ꢃ
/
10ꢂ5 mol, Ligand/Rhꢁ
/
13, P(CO)/P(H2)ꢁ
/
1:1, 90 8C, Syngas pressure 5.0 MPa, reaction time 4 h.
of the polyether group in the molecule. As a general rule,
polyether derivatives are mixtures of different weight
compounds, in which weight distribution is in accor-
dance with Poisson distribution. As elucidated in Table
1, lower weight phosphites have higher solubility in
solvent than higher phosphites as far as OPGPP is
concerned. With successive dissolution of lower phos-
phites in the reaction mixture, higher phosphite retained
to be lost in later reaction runs. After several reaction
runs, loss of P decreased to some extent since higher
phosphites have a slight solubility in heptane. Hence,
although total P-loss from the first run to the seventh
run is somewhat too large from a practical viewpoint,
this polyether phosphite OPGPP demonstrated its
merits for its easy synthesis with low price. P recovery
can be improved via pretreatment with solvent before
use. It also made sense that decantation on cooling
temperature will facilitate the catalyst separation and
benefit the recovery of the phosphites and the catalysts.
In comparison, only 71.4% of conversions were
obtained in the third reaction run in aqueousÁ
/
organic
biphasic system. The reason for the decrease in activity
Table 6
Recycling of OPGPP (nꢁ
/
58)/Rh catalyst in the single organic phase reaction system and aqueousÁorganic biphasic reaction system
/
c
P loss in product (%)
Reaction runs Conversion (%) Aldehyde yield (%)
Aldehyde n/iso
P content in product phase (mg mlꢂ1
)
a
One phase
1
2
3
4
5
6
7
99.4
99.3
99.2
96.3
97.3
94.3
93.0
97.6
97.8
95.0
93.0
96.3
90.5
92.4
0.91
0.95
0.95
0.92
0.93
0.97
0.93
60.4350
55.2800
23.3150
18.6350
17.0000
15.1350
7.0650
7.8
7.2
3.05
2.4
2.22
1.98
0.92
b
Two-phase
1
2
3
4
99.5
91.3
83.7
71.4
97.0
91.3
83.7
71.4
0.95
0.95
0.96
0.94
a
Reaction conditions: 1-decene 2.0 ml, heptane 4.0 ml, internal standard 0.3 ml, Rh(acac)(CO)2 1.058ꢃ
/
10ꢂ5 mol, OPGPP/Rhꢁ
13, P(CO)/
/
P(H2)ꢁ
/
1:1, 90 8C, Syngas pressure 5.0 MPa, reaction time 4 h.
b
c
a
1/1, other conditions are the same as .
Vorg/Vwater
Loss of ligand/employed ligand (based on P content).
ꢁ/

88
X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á90
/
after three reaction runs may be attributed to the partial
hydrolysis of the phosphite in the presence of water as
solvent [14,21,22].
Table 8
OPGPP (nꢁ
of the catalyst
/
58)/Ru3(CO)12 catalyzed hydroformylation and recovery
Reaction runs Conversion (%) Aldehyde yield (%) Alcohol (%)
1
2
3
4
96.3
95.4
89.0
87.1
70.0
68.3
63.7
64.5
25.0
26.0
23.1
22.0
2.5. OPGPP/Rh catalyzed hydroformylation of higher
olefins in single organic phase system
The above non-aqueous reaction system has also been
applied in the hydroformylation of other higher olefins
(1-hexene, 1-octene, 1-dodecene, 1-tetradecene) (shown
in Table 7). Under the same conditions, more than 95%
of conversions were obtained.
Reaction conditions: 1-decene 1.0 ml, heptane 2.0 ml, internal
standard 0.3 ml, Ru3(CO)12 0.0072 g, OPGPP 0.64 g, P(CO)/P(H2)ꢁ
1:1, Syngas pressure 5.0 MPa, reaction temperature 130 8C, 9 h.
/
3. Conclusion
2.6. OPGPP/Ru3(CO)12 catalyzed hydroformylation of
1-decene
Polyether phosphites OPGPPs with over 19 ethylene
glycol units have slight solubility in apolar solvent such
as heptane. Accordingly polyether phosphite was em-
ployed as ligand in the rhodium catalyzed non-aqueous
hydroformylation of 1-decene with heptane as solvent in
direction to catalyst separation. The catalysts have
shown high activity and selectivity to aldehydes. In
contrast to previous rhodium complexes modified by
phosphites, the catalysts precipitated from the reaction
mixture after reaction on cooling to room temperature
or lower. The separated catalyst by simple decantation
was reused up to six times without clear decrease in
activity. Complexes OPGPP/Ru3(CO)3 formed in situ
also proved to be a moderate catalyst in the hydro-
formylation of 1-decene in the absence of water. The
catalysts retained considerable activity in the successive
reaction runs. Hence an effective non-aqueous catalytic
reaction system with polyether phosphites OPGPP has
been proposed in the paper. Application of this reaction
system to other water-sensitive reaction is anticipated in
our further research.
Ruthenium complexes have received relatively little
attention in the hydroformylation because of their much
lower activity than rhodium and cobalt complexes and
inevitable hydrogenation of alkenes and aldehydes
caused by the former. However, when ruthenium com-
plexes as a cluster consist of several metal atoms,
activation of the substrates may take place at more
than one metal atom and this can have a profound effect
on the activity. Here we directed our attention to use of
OPGPP/Ru3(CO)12 catalyst formed in situ to non-
aqueous hydroformylation of 1-decene with heptane as
solvent.
In comparison, the above phosphite/Ru3(CO)12 com-
plex demonstrated similar activity and selectivity with
arylphosphite/Ru3(CO)12 previously reported by Wilk-
inson [27] (see Table 8). Under the moderate conditions
(Tꢁ
/
130 8C, Pꢁ5.0 MPa), a conversion as high as
/
96.3% with 70.0% of aldehydes yield is obtainable. From
the results, considerable hydrogenation of aldehydes to
alcohols was determined. Nevertheless, no apparent
hydrogenation of 1-decene was detected in the hydro-
formylation products. After the reaction, the catalysts
precipitated as yellow wax from the reaction mixture
and could be reused in the successive three runs,
retaining considerable activity.
4. Experimental
4.1. General methods
The preparation and purification of materials were
performed under prepurified nitrogen using standard
Schlenk-type techniques. OPGPP was prepared accord-
ing to literature [21,22]. Rh(acac)(CO)2 was from Beijing
Chemical Institute and 1-decene from Fluka; toluene,
heptane, THF, and ether were distilled from sodium
benzophenone ketyl; methylene chloride was distilled
from CaH2. Octanol was treated with sodium and
distilled under prepurified nitrogen.
Table 7
Hydroformylation of higher olefins catalyzed by OPGPP/Rh in the
single organic phase system
Alkene
Conversion (%) Aldehyde yield (%) Aldehyde n/iso
1-Hexene
1-Octene
99.7
99.2
99.4
97.3
96.5
96.0
97.6
96.3
90.5
2.30
1.45
0.91
0.89
0.85
1-Decene
1-Dodecene
1-Tetradecene 94.5
Infrared spectra were recorded on PerkinÁElmer
/
2000. 1H- and 31P-NMR were recorded at 300, 90
MHz, respectively, on a Varian VXR-300s spectrometer.
Chemical shifts are reported in ppm and referenced to
Reaction conditions: olefin 2.0 ml, heptane 4.0 ml, internal standard
0.3 ml, olefin/Rh(acac)(CO)2 (mol)ꢁ1000, OPGPP/Rhꢁ13, P(CO)/
P(H2)ꢁ1:1, 90 8C, Syngas pressure 5.0 MPa, reaction time 4 h.
/
/
/

X. Liu et al. / Journal of Organometallic Chemistry 654 (2002) 83Á
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89
residual deuterated solvent signals for 1H-NMR and
external 85%H3PO4 (dꢁ
0.00) for 31P-NMR. Gas chro-
matography analysis was run on SP-09 instrument (OV-
101) (50 m capillary column, carrier gas: 2.0 atm N2,
FID detector) equipped with a Shimadzu integrator.
Dodecane was used as an internal standard. Mass
spectra were measured on a Finnagant 312/SS 200
GC-Mass spectrometer.
autoclave was pressurized with CO/H2 (1/1), and
brought to the required temperature in a thermostatic
oil bath. After appropriate time, the samples were taken
from the reaction products to be analyzed by GC-MS.
/
Acknowledgements
Inductively Coupled Plasma-Atomic Emission Spec-
troscopy (ICP-AES): PLASMA-SPEC-I echelle style
element scan Inductively Coupled Plasma-Atomic Emis-
sion Spectroscopy (LEEMAN LABS Company). Mea-
sured wavelength: 369.24 nm (Rh); order: 61; signal/
The financial support of the National Nature Science
Foundation of China (Grant Nos. 29792074, 29906001)
and Open Foundation for Youth (Grant No. KF9808) is
gratefully acknowledged. We thank Professor Peng-
Qingji for 31P-NMR analysis and Dalian Bureau of
Checking and Analyzing Goods for ICP-AES analysis.
background ratio: 350; coolant gas (Ar): 12 l minꢂ1
;
integration time: 3 s; detection limit: 10Á
(P).
/
0.02 mg mlꢂ1
4.2. Preparation of Ru3(CO)12 [28]
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/
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