Re-based heterogeneous catalysts for olefin metathesis prepared by surface organometallic chemistry: Reactivity and selectivity

Article abstract of DOI:10.1002/chem.200390119

Herein we describe the catalytic activity of 1, a well-defined Re alkylidene complex supported silica, in the reaction of olefin metathesis. This system is highly active for terminal and internal olefins with initial rates up to 0.7 mol per mol Re per s. It also catalyses the self-metathesis of methyl oleate (MO) without the need of co-catalysts. The turnover numbers can reach up to 900 for MO, which is unprecedented for a heterogeneous Re-based catalyst. Moreover the use of silica as a support can bring major advantages, such as the possibility to use branched olefins like isobutene, which are usually incompatible with alumina-based supports; therefore, the formation of isoamylene from the cross-metathesis of propene and isobutene can be performed. All these results are in sharp contrast to what has been found for other silica- or alumina-supported rhenium oxide systems, which are either completely inactive (silica system) or typically need co-catalysts when functionalised olefins are used. Finally the initiation step corresponds to a cross-metathesis reaction to give a 3:1 mixture of 3,3-dimethylbutene and trans-4,4-dimethylpent-2-ene, and make this catalyst the first generation of well-defined Re-based heterogeneous catalysts.

Full text of DOI:10.1002/chem.200390119

FULL PAPER
Re-Based Heterogeneous Catalysts for Olefin Metathesis Prepared by Surface
Organometallic Chemistry: Reactivity and Selectivity
Mathieu Chabanas, Christophe Cope¬ret,* and Jean-Marie Basset*[a]
Abstract: Herein we describe the cata-
lytic activity of 1, a well-defined Re
alkylidene complex supported silica, in
the reaction of olefin metathesis. This
system is highly active for terminal and
internal olefins with initial rates up to
0.7 mol per mol Re per s. It also cataly-
ses the self-metathesis of methyl oleate
(MO) without the need of co-catalysts.
The turnover numbers can reach up to
900 for MO, which is unprecedented for
can bring major advantages, such as the
possibility to use branched olefins like
isobutene, which are usually incompat-
ible with alumina-based supports; there-
fore, the formation of isoamylene from
the cross-metathesis of propene and
isobutene can be performed. All these
results are in sharp contrast to what has
been found for other silica- or alumina-
supported rhenium oxide systems, which
are either completely inactive (silica
system) or typically need co-catalysts
when functionalised olefins are used.
Finally the initiation step corresponds to
a cross-metathesis reaction to give a 3:1
mixture of 3,3-dimethylbutene and
trans-4,4-dimethylpent-2-ene, and make
this catalyst the first generation of well-
defined Re-based heterogeneous cata-
lysts.
Keywords: functionalized olefins ¥
heterogeneous catalysis ¥ metathesis
¥ rhenium ¥ silica
a
heterogeneous Re-based catalyst.
Moreover the use of silica as a support
moderate temperature, and can be compatible with functional
groups when activated with organotin agents,[7] while Mo- or
W-based heterogeneous catalysts typically work at relatively
high temperatures (250 4008C) and are usually not compat-
ible with functionalised olefins.[2] One of the reasons for the
difficulty of improving this interesting system is the very small
number of active sites (typically less than 2%);[8] this makes it
difficult to obtain the structure activity relationship.[9] All
these parameters taken together probably explain why it has
been so difficult to improve this system at least if one
compares this heterogeneous catalyst with its homogeneous
competitors. Therefore, it would be highly desirable to
generate, on a surface, ™single-site∫ Re-based catalysts that
can be understood at a molecular level and thereby be
improved by a rational approach.
We and others have been developing a series of well-
defined single-site heterogeneous catalysts for various appli-
cations in catalysis, by using the concepts and tools of surface
organometallic chemistry.[10] By this kind of approach, one
designs and constructs the active site on a surface by attaching
the metal centre to the oxide surface through a covalent (or
ionic, or both) bond(s); these metal centres will have the
necessary ligands to achieve the desired catalytic reaction.
When applied to olefin metathesis the active site should be
attached to the surface of a support through at least a covalent
bond and contain a metallocarbene moiety in order to enter
directly in the catalytic cycle (simple initiation step).
Introduction
Olefin metathesis was discovered more than 30 years ago by
investigating the reactivity of olefin/alkane mixtures on Mo
heterogeneous catalysts.[1, 2] The mechanistic understanding
was a matter of a long debate in the chemical community of
homogeneous catalysis and organometallic chemistry. The
carbene mechanism initially proposed by Chauvin is now well
accepted.[3] This mechanism gave rise to a tremendous effort
in generating well-defined metallocarbenes of the Fischer and
later Schrock types;[4] these were found to be highly active on
their own. They have recently become more and more
tolerant to functional groups and are now compatible with
the needs of organic synthesis.[5] Although heterogeneous
metathesis catalysts have been used commercially at a much
larger scale than their homogeneous analogues (see, for
example, the SHOP or the Phillips processes), little improve-
ment has been achieved in their synthesis and performance.
Even though the extremely active Re2O7/Al2O3 system was
discovered in 1965, it is not yet used commercially to our
knowledge.[6] This system has the advantage of working at
¬
[a] Dr. C. Coperet, Dr. J.-M. Basset, M. Chabanas
¬
Laboratoire de Chimie Organometallique de Surface
UMR-9986 CNRS ESCPE Lyon
43 bd du 11 Novembre 1918
69626 Villeurbanne Cedex (France)
Fax : (‡33)4-72-43-17-95
After considering various existing olefin metathesis cata-
lysts developed both in homogenous and heterogeneous
E-mail: coperet@cpe.fr
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¬
C. Coperet, J.-M. Basset, M. Chabanas
FULL PAPER
catalysis,[2] we have recently developed
a
1,
well-defined
clobutane intermediate: equatorial equatorial (e,e) interac-
tions (formation of the trans product) versus equatorial axial
(e,a) interactions (formation of the cis product).[13] During this
reaction, neopentyl-containing products, namely 3,3-dime-
thylbutene and 4,4-dimethylpent-2-ene, also appear as an 1:3
mixture; this ratio is also compatible with the relative stability
of the possible metallacyclobutane intermediates (Scheme 1),
that is, by avoiding 1,2-interactions and minimising 1,3-
interactions. These products arise from the initiation step,
which is clearly a cross-metathesis. Note that for classical
heterogeneous catalysts this initiation step is often difficult to
understand, and for the Re2O7/Al203 system it is still a matter
of debate.
ꢀ
rhenium carbene
surface
complex
[( SiO)-
ꢀ
ˆ
Re( CtBu)( CHtBu)(CH2tBu)] supported on silica, that has
been fully characterised.[11] Herein we would like to discuss its
unprecedented reactivity in olefin metathesis and compared it
with its classical heterogeneous catalyst competitors.
Results and Discussion
Bringing propene (500 equiv) into contact with 1 in a batch
reactor produces a thermodynamic mixture within two hours
with an initial rate of 0.25 mol
per mol Re per s, which is
tBu
somewhat higher than that re-
ported for Re-based heteroge-
tBu
a)
Re
Me
Me
O
neous catalysts supported on
alumina (Figure 1a). The activ-
ity is higher by a factor of about
103 than that observed with
tBu
[Re]
[Re]
Me
Me
Me
Me
[Re]
R'
[Re]
[Re]
kZ
1e
1e
Si
2a
+
+
+
+
O
Me
Me
O
O
1
classical silica supported Re
2e
Me
[Re]
kE
catalysts.[12] Note that the E/Z
ratio at low conversions in but-2-enes is neither the thermo-
dynamic ratio (3:1) nor the statistical one (1:1), and probably
corresponds to the true selectivity of the catalyst (2.5:1,
Figure 1b). If the relative stability of the metallacyclobutane
intermediates determines the stereochemical outcome of the
reaction, the formation of trans but-2-ene is favoured by
minimising 1,2-interactions in the corresponding metallacy-
Me
Me
Me
b)
tBu
[Re]
tBu
tBu
tBu
1e
[Re]
Me
[Re]
k[1,3]
+
+
+
+
Me
3e
Me
tBu
2e
[Re]
tBu
1e
[Re]
k[1,2]
[Re]
Me
Me
Me
Scheme 1. a) Selectivity in metathesis of terminal olefins governed by 1,2-
interactions in the rhenacyclobutane intermediate. b) Selectivity in initia-
tion products (cross-metathesis with propene).
Additionally, cis-hept-3-ene (1000 equiv) as 1.2m solution
in dichlorobenzene is equilibrated in 8 h at 258C into a 1:1
mixture of hex-3-enes and oct-4-enes with an initial rate of
0.7 mol per mol Re per s (Figure 2). It is worth noting that the
E/Z ratios for hex-3-enes and oct-4-enes are 0.75 and 0.6,
respectively, and are constant up to 45% conversion. Then the
thermodynamic equilibrium is reached as conversion pro-
ceeds (7:1 E/Z ratio). This partial retention of configuration
can also be related to the relative stability of the metal-
lacyclobutane intermediates, which is governed by the min-
imisation of 1,3-interactions (Scheme 2).[13] Moreover these
constant E/Z ratios show that hex-3-enes and oct-4-enes are
the primary products over a large conversion for this system.
This catalyst can also achieve the self-metathesis of
isobutene to 2,3-dimethylbut-2-ene, albeit with a slow rate
(10À4 mol per mol Re per s). Interestingly, both initiation
products, 3,3-dimethylbutene (R' ˆ tBu; R ˆ H) and 2,4,4-
trimethylpent-2-ene (R' ˆ tBu; R ˆ CH3), are obtained in a
1:3 ratio in agreement with the easier formation of a
methylene rather than an isopropylidene carbene intermedi-
ate (Scheme 3). While this reaction is highly endothermic
Figure 1. a) Propene metathesis (500 equiv) catalysed by 1 (1 equiv) at
258C. Evolution of products as a function of time. x ˆ cross-metathesis
products (3,3-dimethylbutene and (E)-4,4-dimethylpent-2-ene) in mol
products per mol Re. y ˆ propene metathesis products in mol product
per mol Re. b) E/Z ratio in the formation of but-2-enes as a function of
conversion of propene.
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Olefin Metathesis
971 975
propene and the cross-metathesis of propene and isobutene;
these reactions lead to an equilibrated mixture of ethylene
(10%), propylene (29%), but-2-enes (4.5% as a 3:1 E/Z
mixtures), isobutene (51%) and 2-methylpent-2-ene (3.5%),
the cross-metathesis product of propene and isobutene. Note
that isobutene does not give clean reactions on classical Re207/
Al2O3 catalyst due to cationic-promoted side reactions
(oligomerisation of isobutene).[14]
These promising results led us to investigate the reactivity
of 1 towards functionalised olefins. Therefore the metathesis
reaction of methyl oleate, a typical test substrate in hetero-
geneous catalysis, was attempted (Figure 3). When 100 equiv-
Figure 2. (Z)-Hept-3-ene metathesis (1000 equiv) catalysed by 1. a) Con-
version versus time. b) E/Z ratio versus conversion.
R
R
[Re]
R'
R
R
R
R
[Re]
R'
[Re]
R'
kZ
1e
3e
2
+
+
+
+
R
R
R
[Re]
R'
2
R
[Re]
R'
olefin governed by 1,3-
kE
[Re]
1e
3a
R
R
R'
Figure 3. Methyl oleate metathesis (100 equiv) catalysed by 1. a) Product
formation [mol product per mol Re] (y) versus time. b) Conversion versus
time.
Scheme 2. Selectivity in metathesis of
interactions of the rhenacyclobutane intermediate.
a
Z
(17.3 kJmolÀ1), the cross-metathesis of propene and isobutene
is more favoured (7 kJmolÀ1). Therefore upon contact of
isobutene (500 equiv) and propene (500 equiv) with 1 at 258C
two parallel reactions are observed: the self-metathesis of
alents of methyl oleate, as a 0.12m solution in dichloroben-
zene, was brought into contact with 1 at 258C, the thermody-
namic equilibrium was reached within 1 h to give a 1:1 mixture
of 9-octadecenes and dimethyl 9-octadecendioates [Eq. (1)].
The use of toluene or pentane
as solvents provided similar
results (Table 1). Noteworthy
+
+
+
2
is the use of THF, which still
∆G = 17.3 kJ/mol
∆G = 7.0 kJ/mol
allows the reaction to take
place, albeit with a much slower
rate. The solvent also has an
influence on the selectivity:
THF and toluene, for example,
give the highest selectivity in
the Z isomer (retention of con-
figuration). Moreover when
2000 equiv of methyl oleate
(1.2m solution in toluene) are
brought into contact with 1, the
R'
R
2
[Re]
R'
R'
R'
[Re]
k[1,2]
[Re]
[Re]
1e
1e
+
R
+
+
R
H
H
R
R
R
R'
[Re]
R
R'
k[1,3]
[Re]
+
R
3a
R
R
R
R
Scheme 3. Self- and cross-metathesis reaction with isobutene. Selectivity in the metathesis of isobutene.
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C. Coperet, J.-M. Basset, M. Chabanas
FULL PAPER
have been outstanding,[5, 17] and
this well-defined Re-based sys-
tem supported on silica is prob-
ably a first step towards the
rational development of highly
active and functional group
compatible heterogeneous cat-
alysts by a molecular approach
of the construction of the active site.
Table 1. Self-metathesis
of
methyl
oleate
catalysed
by
1,
ˆ
ˆ
ꢀ
[( SiO)Re(CH2tBu)( CHtBu)( CtBu)], at 258C. Initial turn-over fre-
quencies and initial diastereoselectivities in various solvents.[a]
Solvent
Initial TOF [sÀ1] (TON)
(E/Z)0 ratio[b]
Experimental Section
THF
o-dichlorobenzene
toluene
< 0.002 (18)[c]
0.07 (50)[d]
0.08 (50)[d]
0.11 (50)[d]
0.05 0.2
0.6 0.7
0.2 0.4
0.6 0.9
General procedure: The silica-supported complex 1 was prepared by using
the literature procedure.[11] All catalytic tests were carried out under an
inert atmosphere either using standard Schlenk techniques (gaseous
reactants) or a glove-box (liquid reactants). Gaseous reactants, that is
propene (Air Liquide), isobutene (Air Liquide), were dried over freshly
regenerated molecular sieves (3 ä) and BTS traps (Fluka) before addition.
(Z)-3-Heptene (96%, Aldrich) was distilled under Ar over CaH2. (E)-5-
Decene (99%, Aldrich) was degassed with four freeze pump thaw
cycles, and dried over freshly activated molecular sieves (3 ä). Methyl
oleate (99%, Aldrich) was used as received unless otherwise specified.
THF was distilled under N2 over Na/benzophenone before use. o-
Dichlorobenzene and toluene were distilled and stored over molecular
sieves (3 ä). Octane was distilled and stored over Na. Octadecane (99%,
Aldrich) was used as received. GC analysis of light alkenes or alkanes (C1
C9) were performed on a gas chromatograph HP5890, equipped with a
flame ionisation detector (FID) and a KCl/Al2O3 on fused silica column
(50 m  0.32 mm). Products of methyl oleate self- or cross-metathesis were
analysed by using either a HP6890 apparatus (HP-1 column, 30 m Â
0.32 mm) or a HP5890 apparatus (HP-5 column).
octane
[a] Experimental conditions: A 0.12m solution (100 equiv) was brought
into contact with 1 at 258C and analysed over time. [b] Selectivity at low
conversions. [c] The reaction was stopped at 18 TON. [d] Equilibrium was
reached.
thermodynamic equilibrium is almost reached, and a turnover
number of 900 (TON) is obtained. Note that classical
heterogeneous catalysts supported on alumina (or silica
alumina) even when activated by tin reagents typically give
25 160 TON.[2, 7, 15] Note also that no system supported on
silica has been reported for the conversion of methyl oleate,
while the closest homogeneous catalyst analogue [{RF6O}2-
[16]
ˆ
ꢀ
Re( CHtBu)( CtBu)] reaches 25 TON.
Metathesis of propene catalysed by 1: The complex 1 (20.4 mmol, 80 mg,
4.75%wt Re) was introduced under Ar in a 381 mL batch reactor. After
evacuation of the gas phase, propene (P ˆ 666 hPa, 10 mmol) was added.
During the reaction at 258C, aliquots were expended in a small volume,
brought to atmospheric pressure and analysed by GC (see Figure 1).
With this system, it is also possible to carry out cross-
metathesis reactions. For instance, a 2:1 ratio of trans-5-
decene (200 equiv) and methyl oleate (100 equiv) was con-
verted within 3 h to the thermodynamic equilibrium (80%
conversion) and with a 80% selectivity in the cross-metathesis
product [Eq. (2)].
Metathesis of (Z)-hept-3-ene catalysed by 1: A 1.23m solution of (Z)-hept-
3-ene in o-dichlorobenzene, containing heptane as internal standard, was
prepared and dried over freshly acti-
vated molecular sieves (3 ä). The sur-
face complex 1 (20 mg, 4%wt Re,
4.3 mmol) was placed in a 5 mL batch
reactor equipped with a conical mag-
netic stirring bar. The reactor was
closed with a cap equipped with a
Teflon septum. At t ˆ 0, the (Z)-hept-
3-ene solution (3.5 mL, 4.3 mmol) was
added at 258C under vigorous stirring
by syringe through the septum. During
the reaction at 258C, aliquots (1
2
drops) were taken, diluted in pure o-
dichlorobenzene (0.2 mL) and ana-
lysed by GC (see Figure 2).
Metathesis of isobutene catalysed by
1: The surface complex
1 (80 mg,
4.75%wt Re, 20.4 mmol) was intro-
duced under Ar in a 381 mL batch
reactor. After evacuation of the gas phase, isobutene (P ˆ 666 hPa,
10 mmol) was added. During the reaction at 258C, aliquots were expended
in a small volume, brought to atmospheric pressure and analysed by GC
(see text).
Conclusion
We have shown that the well-defined Re carbene supported
on silica is a highly active olefin metathesis catalyst even for
functionalised olefins. Moreover this surface complex 1
readily converts ester-containing olefins without the need
for a co-catalyst(s); this is a challenge that has been difficult so
far for both homogenous and heterogeneous Re-based
catalysts. The recent improvements of the Ru-based systems
Propene isobutene cross-metathesis catalysed by 1: The surface complex
1 (40 mg, 4.75%wt Re, 10.2 mmol) was introduced under Ar in a 381 mL
batch reactor. After evacuation of the gas phase, isobutene (P ˆ 333 hPa,
5.12 mmol) and propene (P ˆ 333 hPa, 5.12 mmol) were added. During the
reaction at 258C, aliquots were expended in a small volume, brought to
atmospheric pressure and analysed by GC (see text).
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Olefin Metathesis
971 975
General procedure for the metathesis of methyl oleate: A solution of
[2] For a comprehensive review: In Olefin Metathesis and Metathesis
Polymerization (Eds. K. J. Ivin, J. C. Mol), Academic Press, San
Diego, 1997.
known concentration of methyl oleate in
a solvent that contained
octadecane as an internal standard was prepared, degassed with four
freeze pump thaw cycles and dried over freshly activated molecular
sieves (3 ä). The surface complex 1 (4.3 mmol) was placed in a 5 mL batch
reactor equipped with a magnetic stirring bar. The reactor was closed with a
cap equipped with a Teflon septum. At t ˆ 0, the methyl oleate solution
(3.5 mL) was added at 258C under vigorous stirring by syringe through the
septum. During the reaction at 258C, aliquots (1 2 drops) were taken,
diluted in pure solvent (0.2 mL) and analysed by GC.
¬
[3] J.-L. Herisson, Y. Chauvin, Makromol. Chem. 1971, 141, 161.
[4] a) W. R. Kroll, G. Doyle, J. Chem. Soc. Chem. Commun. 1971, 839;
b) C. P. Casey, T. J. Burkhardt, J. Am. Chem. Soc. 1973, 95, 5833;
c) T. J. Katz, S. J. Lee, Tetrahedron Lett. 1976, 4247; d) For a review on
alkylidene complexes, see: R. R. Schrock, Chem. Rev. 2002, 102, 145.
[5] Review on olefin metathesis for homogeneous catalysis: a) T. M.
Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18; b) R. R. Schrock,
A. H. Hoveyda, Chem. Eur. J. 2001, 7, 945.
[6] a) E. J. Howman, L. Turner, NL Patent, 6605328, 1966; b) J. Cosyns, J.
Chodorge, D. Commereuc, B. Torck, Hydrocarbon Process. 1998, 60.
[7] a) E. Verkuijlen, F. Kapteijn, J. C. Mol, C. Boelhouwer, J. Chem. Soc.
Chem. Commun. 1977, 198; b) M. Sibeijn, J. C. Mol, Appl. Catal. 1991,
67, 279; c) J. C. Mol, Green Chem. 2002, 4, 5.
Metathesis of methyl oleate (100 equiv in o-dichlorobenzene): The general
procedure was followed with 3.5 mL of a 0.123m solution of methyl oleate
in o-dichlorobenzene.
Metathesis of methyl oleate (100 equiv in THF) catalysed by 1: The general
procedure was followed with 3.5 mL of a 0.123m solution of methyl oleate
in THF and 1 as catalyst.
[8] a) F. Kapteijn, H. L. G. Bredt, E. Homburg, J. C. Mol, Ind. Eng. Chem.
Prod. Res. Dev. 1981, 20, 457; b) Y. Chauvin, D. Commereuc, J. Chem.
Soc. Chem. Commun. 1992, 462.
Metathesis of methyl oleate (100 equiv in toluene) catalysed by 1: The
general procedure was followed with 3.5 mL of a 0.123m solution of methyl
oleate in toluene and 1 as catalyst.
[9] J. C. Mol, Catal. Today 1999, 51, 289.
Metathesis of methyl oleate (100 equiv in octane) catalysed by 1: The
general procedure was followed with 3.5 mL of a 0.123m solution of methyl
oleate in octane and 1 as catalyst.
¬
[10] C. Coperet, M. Chabanas, R. Petroff Saint-Arroman, J.-M. Basset,
Angew. Chem. 2003, 115, 164; Angew. Chem. Int. Ed. 2003, 42, 156.
[11] a) M. Chabanas, A. Baudouin, C. Coperet, J.-M. Basset, J. Am. Chem.
¬
Soc. 2001, 123, 2062; b) A. Lesage, L. Emsley, M. Chabanas, C.
Metathesis of methyl oleate (2000 equiv in toluene) catalysed by 1: The
general procedure was followed with 3.5 mL of a 1.23m solution of methyl
oleate (see purification below) in toluene and 1. However, the amount of
catalyst was halved: 2.15 mmol Re (10 mg of 1, 4%wt) in place of 4.3 mmol.
Purification of the methyl oleate was performed as follows: alumina
(0.75 g) was dried 3 h in an oven at 1408C and then dried at 258C under
high vacuum for 2 h. Commercial methyl oleate (4.6 g) and pentane were
added and the mixture was stirred at 258C for 20 min. The methyl oleate
solution in pentane was then filtered through Celite. Pentane was
evaporated in high vacuum leaving pure methyl oleate, which was used
to prepared a 1.23m methyl oleate solution in toluene: methyl oleate
(3.64 g, 12.3 mmol), octadecane (0.423 g, 1.66 mmol) and completion with
toluene to a total volume of 10.0 mL. This solution was degassed and dried
over molecular sieves (3 ä).
¬
Coperet, J.-M. Basset, Angew. Chem. 2002, 114, 4717; Angew. Chem.
¬
Int. Ed. 2002, 41, 4535; c) M. Chabanas, C. Coperet, A. Baudouin, J.-
M. Basset, W. Lukens, A. Lesage, L. Emsley, J. Am. Chem. Soc. 2003,
125, 492.
[12] The activity of rhenium oxides supported on silica is usually poor
under 1208C. For some examples, see: a) A. W. Aldag, C. J. Lin, A.
Clark, Recl. Trav. Chim. Pays-Bas, 1977, 96, M27; b) N. Tsuda, A.
Fujimori, J. Catal. 1981, 69, 410; c) L. G. Duquette, R. C. Cieslinski,
C. H. Jung, P. E. Garrou, J. Catal. 1984, 90, 362; d) P. S. Kirlin, B. C.
Gates, J. Chem. Soc. Chem. Commun. 1985, 277; e) R. M. Edreva-
Kardjieva, A. A. Andreev, J. Catal. 1986, 97, 321.
[13] a) J. L. Bilhou, J.-M. Basset, R. Mutin, W. F. Graydon, J. Chem. Soc.
Chem. Commun. 1976, 23, 970; b) J. L. Bilhou, J.-M. Basset, R. Mutin,
W. F. Graydon, J. Am. Chem. Soc. 1977, 99, 4083.
[14] a) R. Nakamura, H. Iida, E. Echigoya, Chem. Lett. 1972, 273; b) W.
von Siegfried, G. Puetz, Chem.-Ztg. 1988, 15; c) T. Kawai, M. Furuki,
T. Ishikawa, J. Mol. Catal. 1994, 90, 1.
[15] For examples of Re oxide on other supports, see also: a) W. A.
Herrmann, W. Wagner, U. N. Flessner, U. Volkhardt, H. Komber,
Angew. Chem. 1991, 103, 1704; Angew. Chem. Int. Ed. Engl. 1991, 30,
1636; b) R. Buffon, A. Auroux, F. Lefebvre, M. Leconte, A. Choplin,
J.-M. Basset, W. A. Herrmann, J. Mol. Catal. 1992, 76, 287 95; c) R.
Buffon, A. Choplin, M. Leconte, J.-M. Basset, R. Touroude, W. A.
Herrmann, J. Mol. Catal. 1992, 72, L7 10.
Cross-metathesis of a methyl oleate/(E)-dec-5-ene mixture catalysed by 1:
A 0.124m solution of methyl oleate in toluene was prepared, degassed with
four freeze pump thaw cycles, and dried over freshly activated molecular
sieves (3 ä). The surface complex 1 (20 mg, 4%wt Re, 4.3 mmol) was placed
in a 5 mL batch reactor and (E)-5-decene (170 mL, 8.97 Â 10À4 mol) was
added by a precision syringe. The reactor was then closed with a cap that
had a Teflon septum and the methyl oleate solution (3.5 mL, 4.34 10À4 mol)
was added at 258C under vigorous stirring (t ˆ 0) by syringe through the
septum. During the reaction at 258C, aliquots (1 2 drops) were taken,
diluted in pure solvent (0.2 mL) and analysed by GC.
[16] For the synthesis and the use of d0 Re alkylidene complexes as
homogenous catalyst precursors for olefin metathesis, see: a) R.
Toreki, R. R. Schrock, J. Am. Chem. Soc. 1990, 112, 2448; b) R.
Toreki, R. R. Schrock, M. G. Vale, J. Am. Chem. Soc. 1991, 113, 3610;
c) M. H. Schofield, R. R. Schrock, L. Y. Park, Organometallics 1991,
10, 1844; d) R. Toreki, G. A. Vaughan, R. R. Schrock, W. M. Davis, J.
Am. Chem. Soc. 1993, 115, 127; e) G. A. Vaughan, R. Toreki, R. R.
Schrock, W. M. Davis, J. Am. Chem. Soc. 1993, 115, 2980; f) A. M.
LaPointe, R. R. Schrock, Organometallics 1995, 14, 1875; g) B. T.
Flatt, R. H. Grubbs, R. L. Blanski, J. C. Calabrese, J. Feldman,
Organometallics 1994, 13, 2728; h) D. Commereuc, J. Chem. Soc.
Chem. Commun. 1995, 791.
Acknowledgement
We are indebted to the CNRS, and ESCPE Lyon for financial support. M.C.
is grateful to the French Ministry for Research and Education for a pre-
doctoral fellowship. We also would like to thank Dr. Y. Chauvin for helpful
discussions.
[1] a) H. S. Euleterio, US Patent, 3074918, 1963; b) R. L. Banks, G. C.
Bailey, Ind. Eng. Chem. Prod. Res. Dev. 1964, 3, 170; c) In fact there is
earlier evidence for that the discovery of that reaction in polymer
chemistry (ROMP): A. W. Anderson, N. G. Merckling, US Patent
2721189, 1955; I. M. Robinson, L. H. Rombach, W. L. Truett, US
Patent 2932630, 1960; W. L. Truett, D. R. Johnson, I. M. Robinson,
B. A. Montague, J. Am. Chem. Soc. 1960, 82, 2337.
[17] M. B. Dinger, J. C. Mol, Adv. Synth. Catal. 2002, 344, 671.
Received: October 28, 2002 [F4532]
Chem. Eur. J. 2003, 9, No. 4
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