Olefins isomerization by hydride-complexes of ruthenium

Article abstract of DOI:10.1016/j.molcata.2006.02.066

Several complexes containing the Ru-H bond were synthesized according to previous reports: RuH(NO)(PPh₃)₃(I) (1), RuHCl(PPh₃)₃(s)(II) (2), RuHCl(CO)(PPh₃)₃(II) (3), RuH(CH₃COO)(P

Full text of DOI:10.1016/j.molcata.2006.02.066

Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
Olefins isomerization by hydride-complexes of ruthenium
∗
Chuan Jun Yue, Ying Liu, Ren He
Key State laboratory of Fine Chemical, Dalian University of Technology, Liaoning, China
Received 24 January 2006; received in revised form 23 February 2006; accepted 23 February 2006
Available online 13 July 2006
Abstract
Several complexes containing the Ru–H bond were synthesized according to previous reports: RuH(NO)(PPh
3
)
3
(I) (1), RuHCl(PPh
(II)(5), andcharacterizedby HNMRandIRspectra;thecomplex
(s) was screened for further investigation on the basis of activity and life-operating on isomerization of 1-hexene and 1-octadecene
in temperature; the influence of temperature, reaction time and catalyst concentration on 1-hexene isomerization by RuHCl(PPh (s) was carefully
3 3
) (s)(II) (2),
1
RuHCl(CO)(PPh
3 3 3 3 3 2 3 3
) (II)(3), RuH(CH COO)(PPh ) (II)(4)andRuH (CO)(PPh )
of RuHCl(PPh )
3 3
3 3
)
−
5
studied: 1-hexene was converted into other two isomers of 19.39% 2-hexene and 78.16% 3-hexene on the condition of catalyst 2 × 10 mol (in 1 ml
◦
toluene), temperature 120 C, time 30 min, 1-hexene 4 ml; while the performance on 1-octadecene isomerization by RuHCl(PPh
3
)
3
(s) presented
◦
high activity, thermal stability and the solvent-free system: at 180 C the equilibrium conversion of 1-octadecene reached above 94.6% with the
condition of the 1:200 (mol) ratio of catalyst to substrate; and the distinct differences were presented on the isomerization by RuHCl(PPh
for 1-hexene and 1-octadecene in reaction temperature, solvent, intermediate. The evidence on isomerization of 1-hexene and 1-octadcene by
RuHCl(PPh (s) was provided to recognize the specifically isomerization process: the catalytic property was closely relation with coordination
circumference of the centre metal, ligand property and substrate structure, and the mechanism was carefully studied on 2 as well.
2006 Elsevier B.V. All rights reserved.
3 3
) (s)
3 3
)
©
Keywords: Hydride-complexes of ruthenium; RuHCl(PPh3)3(s); 1-Hexene; 1-Octadecene; Isomerization; Process
1
. Introduction
coordination geometries in each electron configuration [3]; it
was always presented that the catalytic activity and selectivity
were different from particular reaction system in light of ligand
property, stereo effect and reaction condition, for instance, the
complex RuHCl(PPh3)3 could not only catalyze isomerization
reaction, hydrogenation reaction, hydrogen transfer reaction [4]
and so on, also was active species for the hydrogenation of the
double bond using RuCl2(PPh3)3 as the catalyst [5].
Isomerization reaction (Scheme 1) is an example of atom
economy in view of green chemistry and one of the most impor-
tant types of reaction in organometallic chemistry. Alkene iso-
merization from double bond migration was catalyzed by many
transition metal complexes like Fe, Co, Pd, Ru, Ni, Rh, Ti, and so
on[6]sofarauptothepresent, thetypeoftheisomerizationfrom
the double migration is generalized as follows: the simply olefin
isomerization [7], the diene isomerization [8], the functional iso-
merization [9] and the isomerization between molecules or in
single molecule (including cycloisomerization) [10], and more
thereactioncanprovideaplentyofvaluablechemicals[11], such
as all kinds of olefin products and their derivatives; in addition
it was well applied to organic synthesis [12] for the examples
of some terpene difficultly synthesized by the classic functional
Transition metal hydrides are important not only in
organometallic chemistry but also in organic synthesis [1],
recently the area has being attracted and rapidly developed on
catalytic reactions with the feature of high activity and selectiv-
ity, mild reaction condition and substrate generality as well as
the reaction process studied easily (homogeneous), some types
of reaction is enumerated in this respect: the activating reac-
tion of C–H bond and C–C bond, hydroformylation of olefin,
hydrogenation of double bond, telomerisation of olefins and
dienes, hydrosilication reaction, hydrogen transfer (TH) and iso-
merization reaction, etc., and being active species was always
detected or proposed in the catalytic process of non-transition-
metal-hydride as precursor, such as complexes of Co, Ni, Pd,
Rh, Fe, Ru [2] among those, the hydride-complexes of ruthe-
nium were in prospect of catalytic reactions due to the wider
scope of oxidation states (from −2 valent to +8) and various
∗
Corresponding author. Tel.: +86 411 8899 3861; fax: +86 411 8363 3080.
E-mail address: Guomengping@yahoo.com.cn (R. He).
1
381-1169/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2006.02.066

1
8
C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
Table 1
Key band data for hydride-complexes Ru on IR and NMR
Complex IR (cm 1)
code
−
1H NMR
Scheme 1. Catalytic isomerization reaction.
transformation route, and the chiral molecule produced [13].
Which involved in the complexes of Rh, Co, Pd, Ni, Pt, Ru;
although there were many catalyst for olefin isomerization now,
respectively, there was some shortage to a certain degree: nickel
complexes always led olefin to the structure isomerization, the
metal (such as cobalt) complexes including carbonyl brought
olefin into formylation, and complexes of Pt, Rh, Pd are of lower
economy than other like ruthenium complexes for the isomer-
ization in those cases; recently it was reported that ruthenium
complexes catalyzed the olefin isomerization [14,15], which
were taken into both catalytic efficiency and economy consid-
eration.
The alkene isomerization from terminal to internal is reason-
able in thermodynamics. Different mechanisms were proposed
for the isomerization process on the basis of different catalytic
systems, reaction conditions and experiment phenomena as well
as data analyzed, and both main ways were suggested: one
was the metal hydride addition–elimination [16] involving the
formationanddecompositionofanalkylmetalcomplexandcon-
stituting a 1,2-hydrogen migration like 1-pentene isomerization
δRu–H (ppm)
2Jp–H (Hz)
1
2
3
4
5
νRu–H: 1966, νN–O: 1640
νRu–H: 1624
−6.7 (q)
30.4
25.6
26.0
28.4
−17.8 (q)
νRu–H: 2020, νCO: 1916, 1900 −18.6 (q)
νRu–H: 2013, νCOO: 1526, 1450 −18.7 (q)
νRu–H: 1960, 1867, νCO: 1940
−6.8 (m), −8.3 (m) 15.2, 28.0
metal ruthenium, ligand type and whether to coordinate satu-
ration to the centre atom Ru. The chemical shifts reflecting the
electron circumstances for the Ru–H band on NMR spectra were
ranked in decreasing order: (1), (5), (2), (3), (4), and the coupling
constants are also distinguished each other, which are beneficial
of realizing the isomerization process.
2
.1. Influence of temperature on olefin isomerization in the
presence of the ruthenium complexes
The data on the catalytic activity of complexes 1–5 in tem-
perature are listed in Table 2.
It indicates that the catalyst 1, 2 are better active than the
others for 1-hexene isomerization, and it was found that the two
catalysts were instauration in view of coordination in itself, how-
ever, on the whole, the conversion of 1-hexene by catalysts above
increases in different degree accompanying the temperature on
the increase; experiment showed that at certain temperature, the
[
17] by the complex RuHCl(PPh3)3; the other was ␲-allyl metal-
hydride intermediate [18] connecting with the hydroformylation
of olefin with the catalyst, and alkyl metal complex decompo-
sition that resulted in a 1,3-hydrogen shift such as 1-pentene
was isomerization [19] by the complex PdCl2(PhCN)2. On the
side, other isomerization mechanisms were introduced in the
literature to explain the phenomena and results such as the tran-
sition metal carbene complex intermediate [20], the dihydrogen
Table 2
Effect of reaction temperature on 1-hexene conversion by hydride-complexes of
Ru
␲
-allyl transition state [21], etc.
In response to the excess surplus for high/low olefin from
◦
olefin oligomerization in industry, the only example was the
famous SHOP [22], in which the Na/K/Al2O3 or MgO system
was used as heterogeneous catalyst to isomerizate high olefin,
and it was presented that operation was inconvenience and oper-
ating life was short, which could not further meet need for better
conversion, no structure isomer and depth which was described
as certain degree of the double bond transfer from terminal to
internal. Since olefin isomerization plays an important role in
both organic synthesis and chemistry industry, we have started
aninvestigationontheisomerizationof1-hexeneand1-octabene
by hydride-complexes of ruthenium.
Temperature ( C)
Catalyst code
Composition (%)
1-Hexene
2-Hexene
3-Hexene
3
5
7
9
0
0
0
0
1
2
3
4
5
39.98
42.38
95.46
98.97
99.64
24.83
24.13
1.83
1.03
0.36
35.19
33.49
2.71
–
–
1
2
3
4
5
38.49
40.47
92.87
98.76
99.46
29.97
32.67
3.93
1.24
0.54
31.54
26.86
3.20
–
–
1
2
3
4
5
31.31
32.53
91.66
80.24
95.75
25.27
29.93
3.99
14.78
1.49
43.42
37.54
4.35
4.98
2.76
2
. Results and discussion
Several hydride-complexes of ruthenium as olefin isomeriza-
tion catalyst were synthesized according to the earlier reports in
the literature: RuH(NO)(PP3)3(I) (1), RuHCl(PPh3)3(s)(II) (2),
RuHCl(CO)(PPh3)3 (II) (3), RuH(CH3COO)(PPh3)3(II) (4),
RuH2(CO)(PPh3)3(II) (5). The characteristic absorption peak
on Infrared and NMR spectra for the complexes 1–5 are listed
in Table 1.
1
2
3
4
5
4.46
5.60
63.05
41.96
87.86
23.48
31.74
20.75
43.90
5.86
72.06
62.66
16.20
14.14
6.28
It is showed that the characteristic absorption peaks on the
Ru–H bond are distinct from the oxidation state of the centre
−5
Conditions: catalyst = 2 × 10 mol; toluene = 1 ml; 1-hexene = 4 ml; t = 30 min;
‘–’: trace.

C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
19
equilibrium was fast established among 1-hexene, 2-hexene and
-hexene, and further implied the process of the metal hydride
the catalytic reaction is fast dynamitic process and establishes
equilibrium in shorter time:
3
addition–elimination in a sense. As for the catalyst 1, isomer-
ization of 1-hexene was mentioned in the literature [23], while
the cause presenting high activity was investigated for 1-hexene
isomerization by the catalyst 2 what follows in the article. In
addition, in order to obtain the satisfying conversion, high tem-
perature is necessary for 1-octadence isomerization using the
catalysts above in that the reaction is high energy barrier, which
was paid attention to and analyzed in the experiment, while by
other catalyst of non-hydride-ruthenium complexes, the con-
version was terribly low with higher temperature frequently.
Unfortunately, the catalyst 1 increasingly became dark the same
as the catalyst 3, 4, 5 during high temperature reaction, which
meant the catalysts inactivation; while the reaction system com-
prising of 2 all the way kept orange in high temperature bath and
presented high thermal stability. So the catalyst 2 was screened
to further study.
◦
And in the other, at 120 C, the conversion of 1-hexene
accompanying the time from 30 to 180 min is fundamentally
kept stable within the error for the gas chorography (Table 4),
exactly, within 1 h the equilibrium has been established to a cer-
1
tain degree, but the products analyzed by H NMR showed that
the transformation between cis- and trans-isomer still existed
which directed the cis-isomer, the result is the same as the liter-
ature [24] reported previously:
trans-2-hexene ꢀ cis-2-hexene,
trans-3-hexene ꢀ cis-3-hexene
And more, the data above is confirmed according to the inte-
grated equation [14]: kt = ln[a0/a0(1 − x)] (a0: the initial con-
centration of 1-hexene, t: the reaction time, x: the percentage
conversion); by calculation, the first-order reaction average rate
2
.2. Influence of reaction parameters for 1-hexene
isomerization by RuHCl(PPh3)3(s)
¯
−2 −1
m . In brief, the reaction time is freely chosen
k is 3.0 × 10
in a certain temperature condition.
2
.2.1. Reaction temperature
The influence of temperature on the catalytic activity of 2 is
listed in Table 2.
It is at the relatively lower temperature that isomerization
began, the conversion of 1-hexene increases from 57.6% at
03 K up to 94.4% at 363 K all linear isomers of 1-hexene were
produced, whichis2-hexene, 3-hexene, andotherproductwasn’t
detected, and their amount goes up close two times when the
temperature was raised from 303 to 363 K. It is presented that
the reaction process is easily adjusted by the catalyst 2 in ther-
modynamic energy:
2
.2.3. Effect catalyst concentration
This aspect of catalyst concentration (in toluene) or the cat-
alyst number (constant solvent amount) is reported in Table 5.
The conversion of 1-hexene rises from 26.97% to 59.75%
which only increases more two times when the catalyst amount
in 1 ml toluene is increased from 1.0 to 15.0 mg which increases
3
1
5 times, and it was finally found that the catalyst solubility
became worse at a temperature if the catalyst amount was added
more; the result is satisfying when the ratio of the hexene to
the catalyst is 2000, which is selected for further research. In
Table 4
◦
Effect of reaction time on 1-hexene conversion by RuHCl(PPh3)3(s) (120 C)
So, in that case the low temperature may be taken into con-
sideration.
Time (h)
Composition (%)
-Hexene
1
2-Hexene
3-Hexene
1
2
.0
.0
2.67
2.64
2.52
2.50
2.46
20.53
20.78
20.24
20.05
19.64
76.80
76.58
77.24
77.45
77.90
2
.2.2. Reaction time
The result of reaction time is obtained to see Table 3.
4.0
.0
1.0
◦
7
1
At 50 C the conversion of 1-hexene increases from 59.5%
to 63.04% when reaction time increases from 30 to 180 min,
which yield does not rise obviously, and it demonstrates that
catalyst = 2 × 10−5 mol;
Conditions:
T = 120 C.
toluene = 1 ml;
1-hexene = 4 ml;
◦
Table 3
Table 5
◦
Effect of reaction time on 1-hexene conversion by RuHCl(PPh3)3(s) (50 C)
Effect of catalyst number on 1-hexene conversion by RuHCl(PPh3)3(s)
Catalyst amount (mg) Composition (%)
-Hexene
Time (min)
Composition (%)
-Hexene
1
2-Hexene
3-Hexene
1
2-Hexene
3-Hexene
3
6
9
20
80
0
0
0
40.47
40.25
40.14
39.91
39.86
32.67
33.63
33.29
32.57
32.55
26.86
26.13
26.57
27.52
27.59
1
5
0.0
5.0
0.0
.0
.0
90.69
83.14
60.48
53.92
49.98
5.03
9.32
22.74
25.45
27.61
4.28
7.54
16.78
20.63
22.41
1
1
2
1
1
Conditions: catalyst = 2 × 10− mol; toluene = 1 ml; 1-hexene = 4 ml; T = 50 C.
5
◦
◦
Conditions: time = 30 min; toluene = 1 ml; 1-hexene = 4 ml; T = 50 C.

2
0
C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
Table 6
Results of recycling on 1-hexene conversion by RuHCl(PPh3)3(s)
Circling
Composition (%)
-Hexene
1
2-Hexene
3-Hexene
That is obviously different from 1-hexene isomerization: the
system color kept the orange during the reaction, the analysis
by H NMR did not show the peak of the Ru–H bond which
1
2
3
4
5
6
7
42.28
40.91
40.87
42.66
51.27
51.33
60.52
24.18
37.60
32.87
33.27
28.31
28.17
24.57
33.54
21.49
26.26
24.07
20.42
20.50
14.91
1
probably the catalyst concentration containing the Ru–H bond
was too low, but in theory M is stability. While for 1-hexene, the
1
red-violet color doesn’t change all the time, and H NMR spec-
tra could reflect the Ru–H bond, and uncovered that 1-hexene
isomerization is fast process from other side.
Conditions: catalyst = 2 × 10− mol; toluene = 1 ml; 1-hexene = 4 ml added for
5
◦
every time; t = 30 min; T = 50 C.
2.4. Generalization in performance on olefin isomerization
addition, the conversion decreased a little when the catalyst
contained some free triphenyl phosphorus in the experiment,
which demonstrated the competing coordination to the centre
Ru between olefin and PPh3 in catalytic process.
by hydride-complex of Ru
The generalization deriving from experiments observed and
results analyzed is described below:
2
.2.4. Recycling test
The work is usually used to check the catalyst operating life.
Table 6 presents the result of every successive recycle. Dur-
(1) It is a key step whether olefin effectively coordinates with
transition metal complex or not for the reaction to be hap-
pened.
ing the beginning four times recycle, it is presented that the
conversion of 1-hexene is almost the same, and that it’s activity
was kept; the data decreases to a little degree after the fifth and
sixth recycle, thereafter the activity declines to a lager degree,
the causes are as follows: (1) the catalyst color began to change
from red-violet to thin dark-red, and hinted the Ru–H bond in
(2) For a complex, the [Ru]–H activity on isomerization is
closely related to ligands such as category, property, stereo
structure.
(3) The olefin structure as the reaction substrate influences reac-
tion process and equilibrium state to a different degree.
1
catalyst was reduced in a sense, which was confirmed by H
2.5. Primary discussion on mechanism
NMR; (2) the catalyst was lost, that is, one was that the catalyst
was adsorbed by the reactor without in the solvent, the other was
that it was taken away with solvent during the operation of the
evacuation.
The results have presented activity and efficiency on iso-
merization by 2; some causes were investigated: the first-order
reaction rate is listed in Table 7 which also contains the same
reaction catalyzed by RuHCl(PPh3)3(s) which was synthesized
in different method [25,26] early reported and in which the only
difference lies in s (solvent) adsorbed by catalyst, obviously
the catalytic result is here better than ones recorded in previous
work.
2
.3. 1-Octadecene isomerization by RuHCl(PPh3)3(s)
The feature that the complex RuHCl(PPh3)3(s) catalyzed 1-
octadecene isomerization lies in: high activity, thermal stability
◦
and the solvent-free system. At 180 C, equilibrium conversion
Taken into solvent effect consideration, the same result was
acquired when benzene only replaced commensurate toluene as
a solvent on the comparable condition, and thought about poten-
tial species RuH2(PPh3)3 produced in situ, the poor result was
led to on the identical condition when the RuH2(PPh3)3 [24] was
used as olefin isomerization catalyst yet; what’s more, the con-
version what little rose but was not so conspicuous when EtOH
was added to the reaction system successively; furthermore, to
of 1-octadecene got to above 94.60% when the ratio of the cata-
lyst to the substrate was 1:200, the GC spectrum (Fig. 1) shows
one of the isomerization results. In experiment, the process is
thought:
Table 7
The different rate from RuHCl(PPh3)3(s) by different synthesis method for 1-
hexene isomerization
s (in synthesis) Substrate, s (in catalysis) Rate (min 1)
−
Catalyst
RuHCl(PPh3)3
Non
3 × 10− (in H2)
4
<
3.0 × 10−
2
EtOH
Fig. 1. GC Spectrum of 1-octadecene isomerizated.
s: solvent.

C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
21
Fig. 2.
check tracking experiment done by IR, it showed that the absorp-
tion peaks on EtOH were C–O absorption state (Fig. 2(a))) at
−
1
1
025–1040 cm when the system only had catalyst and sol-
vent, while the ones were changed (Fig. 2(b) and (c)) at 0.5
and 1.0 h, respectively, after 1-hexene was added to; otherwise,
the anagogic structure (A or/and B [27]) (Fig. 3) as a transition
state possibly influenced the process, unfortunately the reaction
system could not be probed.
In general, it is supposed ligand exchange which presents
olefin in place of EtOH adsorbed by RuHCl(PPh3)3 is responsi-
ble for the reaction to start fast, and the terminal olefin isomer-
ization is feasible in thermodynamic, which can interpret the
Scheme 2. Mechanism of RuHCl(PPh3)3(s)-catalyzed olefin isomerization.
difference from the same catalyst but the distinguished synthe-
sis method. And being connected with the associated catalytic
performance reported in previous literature [28,29], the below
mechanism proposed (Scheme 2).
3. Conclusion
(
1) Being taken insert–elimination process of olefin isomer-
Fig. 3.
ization into account, several complexes containing the

2
2
C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
Ru–H bond were synthesized according to previous work:
4.2. Preparation of catalysts
RuH(NO)(PPh3)3, RuHCl(PPh3)3(s), RuHCl(CO)(PPh3)3,
RuH(CH3COO)(PPh3)3 and RuH2(CO)(PPh3)3, and the
complex of RuHCl(PPh3)3(s) was screened for further
investigation on the base of activity and life-operating on
isomerization of 1-hexene and 1-octadecene.
Generally considered, experiment, unless otherwise spec-
ified, was operated under a nitrogen atmosphere using the
Schlenk technique.
RuHCl(PPh3)3(s):RuCl2(PPh3)3 (1.91611 g, 2.0 mmo1) and
KOH (0.1120 g, 2.0 mmo1) were placed in a 100 ml Schlenk
flask and purged with nitrogen, dry EtOH (40 ml) was added
by syringe, the brick red suspension system was stirred, and
(
2) The influence of temperature, reaction time, catalyst con-
centration on 1-hexene isomerization by RuHCl(PPh3)3(s)
◦
was studied, at 50 C, 150 mg catalyst (in 1 ml toluene),
◦
1
80 min, the 63.04% conversion of 1-hexene was attained,
then carefully slowly heated till 100 C (bath temperature) to
◦
and in accordance with other condition, at 120 C that
reached 97.54%, further the cis-isomer rose with the reac-
tion time increasing and indicated the better life-operating
in the light of catalytic cycle.
reflux under nitrogen, and during the process, the system color
became from brick red to khaki till purple, the reaction was kept
stirring and refluxing for about 2 h, thereafter the solution was
allowed to coo1 to room temperature, the purple precipitate was
collected in core filter purged by nitrogen, and did filter-pressing
using nitrogen, washed methanol (2 ml × 10 ml) water oxygen-
free (5 ml), and again with methanol and n-hexane (5 ml × 5 ml),
then pressed filter to close dry, and dried in vacuum over silica
gel for a long time the purple powder solid (1.7 g, 91.9%).
Other complexes were prepared according to the pre-
vious literature their spectroscopic characteristics were
in agreement with the data reported: RuH(NO)(PPh3)3
[30], RuHCl(CO)(PPh3)3 [31], RuH(CH3COO)(PPh3)3 [32],
RuH2(CO)(PPh3)3 [33].
(
(
3) The 1-octadecene isomerization by RuHCl(PPh3)3(s) pre-
sented high activity, thermal stability and the solvent-
◦
free system, at 180 C the equilibrium conversion of 1-
octadecene reached above 94.6% with the condition of the
1
:200 ratio of catalyst to substrate.
4) Obvious difference was presented on the isomerization by
RuHCl(PPh3)3(s) for 1-hexene and 1-octadecene: (i) on
temperature for isomerization conversion: the reaction tem-
perature was more higher in 1-octadcene than in 1-hexene,
and more, at lower temperature, 1-octadcene process hardly
proceeded; (ii) on solvent for the isomerization reaction:
the system on 1-hexene was necessary for solvent such as
toluene, benzene, while one on 1-octadecene was without
solvent, and at room temperature the catalyst may better
4.3. Procedures
1
The isomerization reaction of olefin was carried out in a 25 ml
dissolve 1-octadcene; (iii) on intermediate: by H NMR
stainless autoclave with magnetic stirrer, or for 1-octadecene
isomerization was also done in three bottle flask, the autoclave
with weighted catalyst was sealed and displaced with nitrogen
for three times, unsealed and then past through with the nitrogen
stream, other reaction substrate and necessary solvent was added
in by syringe, and sealed again, finally the autoclave was put into
a constant bath, and heated to the desired temperature; after the
expiration of the desired reaction time, the autoclave was taken
out and cooled to room temperature naturally, and hexene mix-
ture was slow distilled and collected, while octadecene mixture
was distilled under reduced pressure with heat.
spectra, the certain intermediate on 1-octadcene isomeriza-
tion was relatively stable, while that was rather reactive in
hexene, which the quick reaction process was interpreted.
5) Evidence on isomerization of 1-hexene and 1-octadcene
by RuHCl(PPh3)3(s) provided to recognize the specifical
process: the catalytic property was closely relation with
coordination circumference of the centre metal, ligand prop-
erty and substrate.
(
(
6) The mechanism was carefully studied; the solvent adsorbed
by the catalyst should be responsible for high activity and
efficiency.
4
. Experimental
4.4. Measurement and analysis
4
.1. Materials
The complexes above were characterized by infrared spectra
measured on the neat condition in a Nicolet 50X FT-IR spec-
trophotometer and H NMR spectra recorded By a Varian/Nova-
Methanol and ethanol were distilled after refluxing over
1
the corresponding magnesium alkoxides under nitrogen atmo-
sphere, triphenyl phosphine recrystallized from purified ethanol,
n-hexane and toluene distilled after refluxing with sodium thread
adding a bit biphenyl ketone under the same nitrogen atmo-
sphere, 1-hexene and water were refluxing for a long time with
nitrogen stream, 1-octadcene (purity: 90%) was degassed by the
replacement of nitrogen under reduced pressure for three times
in froze ethanol bath, sodium acetate was dried with heat for a
long time under reduced pressure, Ruthenium trichlorohydrate
and sodium borohydride were dealt with nitrogen to remove
oxygen before use.
4
00 type spectrometer at 400 MHz, the chemical shifts were
determined in ppm using TMS as internal standard, quantitative
analysesofthereactionproductswereperformedbyaSRI8610C
type gas-chromatograph (length: 60 m), the correcting factors
were introduced in consideration of the isomerization process
to be discussed.
Acknowledgement
This work was supported by China petroleum.

C.J. Yue et al. / Journal of Molecular Catalysis A: Chemical 259 (2006) 17–23
23
References
[17] D.F. Ewing, B. Hudson, D.E. Webster, P.B. Wells, J. Chem. Soc. Dalton
1972) 1287.
(
[
[
18] L. Roos, M. Orchin, J. Am. Chem. Soc. 87 (1965) 5502.
19] H. Hattori, N. Yoshii, K. Tanabe, Proceedings of the 5th International
Congress on Catal. Palm. Beach 1972, North-Holland, Amsterdam, 1973,
p. 233.
20] N.R. Davies, Nature 201 (1964) 490.
21] R.S. Coffey, Tetrahedron Lett. (1965) 3809.
[
[
[
[
[
[
1] H.D. Kaesz, R.B. Saillant, Chem. Rev. (1972) 231–281.
2] R. Noyori, T. Ohkuma, Angew. Chem. Int. Ed. 40 (2001) 40.
3] T. Naota, H. Takaya, S.-I. Murahashi, Chem. Rev. 98 (1998) 2599.
4] E. Mizushima, M. Yamaguchi, T. Ya-Magishi, Chem. Lett. (1997) 237.
5] J. Chatt, Science 160 (1968) 728.
[
[
[
6] (a) H.W. Sternberg, R. Markby, I. Wender, J. Am. Chem. Soc. 78 (1956)
22] R.H. Crabtree, The Organometallic Chemistry of the Transition Elements,
5
704;
2nd ed., Wiley, NY, 1994, pp. 298–299.
(
(
(
(
(
(
(
b) I. Ender, et al., J. Am. Chem. Soc. 78 (1956) 5401;
c) N.R. Davies, Nature (1964) 201490;
[
[
[
23] C. O’Connor, G. Wilkinson, J. Chem. Soc. A (1968) 2665.
24] J.J. Levison, S.D. Robinson, J. Chem. Soc. A (1970) 2947.
25] P.S. Hallan, D. Evans, J.A. Osborn, G. Wilkinson, Chem. Commun. 7
d) J.F. Harrod, A. Chalk, J. Am. Chem. Soc. 86 (1964) 1776;
e) R.D. Cramer, J. Am. Chem. Soc. 88 (1966) 2272;
f) R.E. Rinehart, J.S. Lasky, J. Am. Chem. Soc. 86 (1964) 2516;
g) H. Bestian, K. Clauss, Angew. Chem. Int. Ed. 2 (1963) 704;
h) C.A. Tolman, J. Am. Chem. Soc. 94 (1972) 2994.
(
1967) 305.
26] P.S. Hallan, B.R. McGarvey, G. Wilkinson, J. Chem. Soc. A (1968)
143.
[
3
[
[
27] D.S. Trifan, R. Bacskai, J. Am. Chem. Soc. 82 (1960) 5010.
28] (a) B.R. James, D.K.W. Wang, J. Chem. Soc. Chem. Commun. (1977)
[
[
[
7] R. Cramer, Acc. Chem. Res. 1 (1968) 186.
8] J.E. Arnet, R. Pettit, J. Am. Chem. Soc. 83 (1961) 2954.
9] Y. Sasson, G.L. Rempel, Tetrahedron Lett. 47 (1974) 4133.
5
(
500;
b) S.R. Patil, D.N. Sen, R.V. Chaudhari, J. Mol. Catal. 19 (1983) 233;
S.R. Patil, D.N. Sen, R.V. Chaudhari, J. Mol. Catal. 23 (1984) 51;
[
[
10] M. Sworin, W.L. Neumam, J. Org. Chem. 53 (1988) 4895.
11] W.A. Hermann, in: B. Cornils, W.A. Hermann (Eds.), Applied Homoge-
neous Catalysis with Organometallic Compound, VCH, Weinheim, 1996,
p. 980.
12] M. Franck-Neumann, F. Brion, Angew. Chem. Int. Ed. 18 (1979) 688.
13] M. Kitamura, K. Manabe, R. Noyori, H. Takaya, Tetrahedron Lett. 40
(
(
c) A.M. Stolzenberg, E.L. Muetterties, Organometallics 4 (1985) 1739
therein).
[
29] N.M. Doherty, J.E. Bercaw, J. Am. Chem. Soc. 107 (1985)
670.
[
[
2
[
[
30] C.G. Pierpont, R. Eisenbergm, Inorg. Chem. 11 (1972) 1094.
31] P.S. Hallman, B.R. McGarvey, G. Wilkinson, J. Chem. Soc. A (1968)
(
1987) 4719.
[
[
14] A. Salvini, P. Frediani, F. Piacenti, J. Mol. Catal. A: Chem. 159 (2000) 185.
15] A. Salvini, P. Frediani, F. Piacent, A. Devescovi, J. Organomet. Chem. 625
3143–3150.
[
[
32] L. Vaska, J.W. Diluzio, J. Am. Chem. Soc. 83 (1961) 1262.
33] R.W. Mitchell, A. Spencer, G. Wilkinson, J. Chem. Soc. Dalton (1973) 846.
(
2001) 255.
[
16] R.F. Heck, D.S. Breslow, J. Am. Chem. Soc. 83 (1961) 4023.