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Methyltrioxorhenium as Catalyst for Olefin Metathesis.

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The olefin metathesis is a reaction catalyzed by organometallic compounds, and its significance for the synthesis of
basic and fine-chemical olefins as well as of polymers (polyalkenamers) is steadily increasing.t2331
Variants, including
both homogeneous and heterogenous catalysis, are presently
used in eight technical p r o c e s ~ e s , but
[ ~ ~the
~ ~metathesis
functionalized olefins still presents problems (e.g., high catalyst concentrations, catalyst poisoning). In these cases cocatalysts (preferably alkyltin compounds) are essential, even for
the more active systems (e.g. Re,0,/A1,0,).[2-41
We have now discovered that the title compound MTO
(la) and higher homologues (RReO,, R = alkyl, aryl) on
acidic metal oxide supports form metathesis catalysts that
are active without additives even for functionalized
ole fin^.^^] The K complexes 1b, c and the N-complex 1d are,
however, not suitable. The standard system MTO/Al,O,-
CAS Registry numbers:
la, 137330-26-8; l a . Za, 137429-00-6; la'2b, 137429-02-8; la .2c, 13742903-9; l a . 2j, 137429-01-7; l a . Zk, 137429-04-0; lb, 137330-27-9; l b . Za,
137429-05-1;Zd, 90-12-0; Ze, 91-20-3; Zf,93-04-9; t g , 91-58-7; Zh, 581-89-5;
Zi, 581-43-1; 4 a . Zb, 137330-24-6;4 a . 2j, 137330-25.7; 4b, 137232-96-3;4c,
69770-45-2; 4d, 68359-37-5; 4e, 69770-45-2.
[I] a) W. Stendel, R. Fuchs, Vet. Med. Rev. 1982, 115-129; b) R. Fuchs, I.
Hammann, W. Stendel, DE-A 2730515 (July 6, 1977/January 18, 1979),
Bayer AG.
[2) R. Fuchs, W. Stendel, DE-A 3629387 (August 29, 1986/March 3, 1988),
Bayer AG.
[3] Crystal structure analysis of 3: space group P2,lc (no. 14); a = 2152.2(2),
b = 583.45(8), c = 2388.9(3) pm, p = 82.726(8)", Z(flumethrin) = 4, Z(2,6dimethylnaphthalene) = 2, since this compound is situated on a symmetry
= 1.314 g ~ m - Enraf-Nonius
CAD4 diffractometer, room
center, pralod
temperature, Cu,. radiation, 5054 independent reflections, empirical absorption correction, solution with direct methods. Refinement: anisotropic
temperature factors for non-hydrogen atoms, isotropic temperature factors
for hydrogen atoms; R (3263 reflections, 483 parameters) = 0.040. Further
details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, W-7514 Eggenstein-Leopoldshafen 2 (FRG) on
quoting the depository number CSD-55648, the names of the authors, and
the journal citation.
[4] Drawn with the program SYBYL of Tripos Inc., St. Louis, USA, from
X-ray crystallographic data.
[5] a) F. Vogtle, W. M. Muller, U. Werner, J. Franke, Naturwissenschafren 72
(1985) 155; b ) E Cramer, Angew. Chem. 68 (1956) 115.
[6] S. B. Ferguson, F. Diederich, Angew,. Chem. 98 (1986) 1127; Angew. Chem.
I n l . Ed. EngL 25 (1986) 1127.
[7] a) Composition [wt%] alkylbenzenes (- Cl, ) 23.4; naphthalene 14.2; 2methylnaphthalene 29; I-methylnaphthalene 13.9; 1,6-dimethylnaphthalene 5.2; 2,6-dimethylnaphthalene 4.8; other long-chain alkylnaphthalenes (12-13 C atoms); b) /3-alkylated naphthalenes are also included
preferentially within thiourea inclusion compounds: D. Montgomery, J.
Chem. Eng. Data 8 (1963) 432.
[S] a) D. Worsch, E Vogtle, Top. Curr. Chem. 140 (1987) 21-41; b) F. Toda,
ibid. 140 (1987) 43-69.
[9] K. Naumann in G. Haug, H. Hoffmann (Eds.): Chem. Plnnt Proi. 4 ("Synthetic Pyrethroid Insecticides: Structures and Properties") (1990) 64-66.
l a (MTO)
lb, R = H
l C , R-CH,
SiO, (I) is simple to prepare and the most thoroughly studied. It catalyzes in particular the self-metathesis of ally1
halides, ethers, silanes, and unsaturated carboxylates and nitriles, but also the ethenolysis of olefins with internal double
bonds (Table 1). Catalyst I operates at room temperature
Table 1. MTO-catalyzed self-metathesis and ethenolysis of open-chain olefins [a]
Starting olefin
Methyltrioxorhenium as Catalyst for
Olefin Metathesis **
By Wolfgang A . Herrmann,* Werner Wagner,
Uwe N . Flessner, Ursula Volkhardt, and Hartmut Komber
Dedicated to Professor Karl Heinz Biichel
on the occasion of his 60th birthday
Methyltrioxorhenium (MTO, CH,ReO,) is the most easily accessible organometal oxide. It is prepared from dirhenium heptaoxide and tetramethyltin, may be conveniently purified by vacuum sublimation, is stable far above its melting
point (m.p. 106"C), dissolves in all organic solvents andwater without decomposition, and is stable to air and acid.['' In
addition to these advantageous properties, MTO has exceptional catalyst qualities which we describe in this and the two
subsequent communications.
Prof. Dr. W. A. Herrmann, Dr. W. Wagner ['I, U. N. Flessner, U .
Volkhardt, Dr. H. Komber ["I
Anorganisch-chemisches Institut der Technischen Universitat Miinchen
Lichtenbergstrasse 4, W-8046 Garching (FRG)
New address: Consortium fur Elektro-chemische lndustrie GmbH
Zielstattstrasse 20
W-8000 Munchen 70 (FRG)
Alexander von Humboldt Fellow (lY91). Permanent address: Institut fur
Technologie der Polymere, Hohe Strasse 6, 0-8010 Dresden (FRG)
Multiple Bonds between Main-Group Elements and Transition Metals,
Part 100, first communication. (The second and third communications
follow directly.) This work was supported by the Hoechst AG and the
Fonds der Chemischen Industrie. Part 99: W. A. Herrmann, S. J. Eder,
P. Kiprof, 1 Organomet. Chem. 412 (1991) 407-414.
0 VCH Verlagsgesellschajt mbH,
W-6940 Weinheim, 1991
Yield [%I
Product olefin
100 [b]
[Br(CH,),CH=l, + CH,=CH,
CH,=CH, 80
i) BrCH,CH=CH,
[BrCH,CH=I, + CH,=CH,
k) C,F,,CH=CH,
1) C,F,,CH,CH=CH,
m) C,F,,(CH,),CH=CH2
[C,F,3(CH,)zCH=J, + CH,=CH, 55
n) C,H,O,C(CH,),CH=CH,
41 [bl
+ CH,=CH,
0) CH,(CH,),CH=CH(CH,),COOCH, [CH,(CH,),CH=J,
27 [b, cl
[a] Heterogeneous catalyst MTO on AI,O,-SiO, [S, 61; room temperature. The equilibrium turnover is (absolute) 50% (= 100% of the theoretical turnover). With theexception
of b) and n), closed systems were used. [b] Absolute yields with respect to the starting
olefin. [c] Ethylene pressure: 7 bar.
and is also suitable for the metathesis of simple open-chain
and cyclic olefins (Table 1 and 2). Otherwise frequent side
reactions such as double-bond isomerization and olefin
dimerizationr2] are insignificant in the presence of 1. The
equilibrium in the metathesis of 1- and 2-hexene is established within minutes at 25 "C. For use with suspensions, the
0570-0833/91/1212-1636$3.50+ ,2510
Angew. Chem. Inr. Ed. Engl. 30 (1991) No. 12
solvents dichloromethane and chlorobenzene proved best.
The volume of solvent used seemed not to affect the metathesis equilibrium.
Figures 1 and 2 show that I is a more efficient catalyst than
Re,O,,r’] which for functionalized olefins is active only in
the presence of organotin compounds. In the case of methyl
ESCA) of reduced species (ReV1,ReV)might be catalytically
2) MTO loses maximally 5 % of the organic groups as
methane and ethylene on the preparation of catalyst I. Use
of CD,ReO, (>99% D) confirmed the participation of
metal-coordinated CD, groups in olefin metathesis (formation of CD,=CHC,H, and CD,=CH, from l-butene).
3) Free MTO cannot be separated from the carrier even
under high vacuum at temperatures up to 150°C. At higher
temperatures decomposition accompanied by predominantly methane and ethylene evolution is observed. MTO can
also not be removed from the carrier by solvents. We assume
that MTO is fixed by condensation reactions such as that
represented in the model equation (a).[’]
+ H,O
R = CH,
Fig. 1. Relative productivity of rhenium-containing heterogeneous metathesis
catalysts. determined under standardized test conditions ( 2 5 “C, 60 min, carrier
AI,O,-SiO, 13/87. 3 w t % rhenium charge).
oleate, the conventional catalyst system prepared from
NH,ReO, approaches the activity of the new catalyst I only
when the considerably higher maximum rhenium charge of
about 10 wt % is employed.
Fig. 2 . Relative productivity of heterogeneous catalysts for the metathesis and
ethenolysis of methyl oleate under standardized test conditions ( 2 5 ° C 60 min,
support AI,O,-SIO, 13/87, 3 w t % rhenium charge). Tetramethyltin was used
for activation tet act.").
The special catalyst activity of MTO is lost when the
methyl groups are cleaved. To avoid this degradationldeactivation reaction (which forms methane!), thermally pretreated carriers are required.l6] Besides A120,-containing systems, Nb,O, is suitable.r81Usually the catalyst loading rates
are 1-3 wt% (ca.13 g MTO per kg).
The following picture of the nature and mechanism of the
MTO/Al,O,-SiO, system has been formed from physical
studies of 900 metathesis experiments:
1) ESCA studies reveal that the metal oxidation state (Re””)
is largely maintained on impregnation of the oxide support.
Nevertheless, a very small proportion (not quantifiable by
Angew. Chem. Ini. Ed. Engl. 30 (1991) N o . 12
0 V C H VerlagsgesellschaflmbH,
The condensation reaction increases the Lewis acidity of
the rhenium, as is shown by solid state IR spectroscopy
(diffuse reflectance):[”’ the asymmetric R e 0 stretching
band of catalyst I is shifted by up to 25 cm-’ to shorter
wavelength relative to that of free MTO. This electronic
change at the central atom is also reflected in the increased
moisture sensitivity of catalyst I. Although free MTO is relatively stable in water and acid, the system MTO/AI,O,SiO, is rapidly decomposed on hydrated surfaces to methane,
ethylene, and perrhenate (GC, IR). Perrhenate bonded to the
surface has been detected for the system Re,O,/AI,O, .[“I
MTO is also suitable for use in homogeneous catalyst
systems for olefins that have no functional groups. Thus, the
system MTO/R,AICI,-n (11, R = CH,, C,H,; n = 1, 2) is
very efficient for the metathesis of 2-pentene at room temperature; equilibrium is achieved in less than 5 min (Re:
olefin = 1:loo).
Furthermore, ring-opening polymerization is catalyzed by
the homogeneous catalyst 11, as shown by the example of
norbornene and some derivatives. Within minutes at room
temperature polynorbornene of high molecular weight and
medium polydispersity is formed [Equation (b) and Table 21.
The products are very soluble and have a high proportion of
cis-configurated moieties (up to 84%, Table2). The cisstereoselectivity can be controlled by the rhenium/cocatalyst
ratio: an increase in the organoaluminum component yields
a polymer with a higher proportion of trans-configuration.
However, an eightfold excess of the cocatalyst causes low
molecular weight products and insoluble polymers to form.[’21
Because practically all metathesis catalysts are based on
oxides or halides of molybdenum, tungsten, and rhenium,
MTO introduces-after 30 years of research in this fieldr2]a new generation of structurally defined catalysts. Even
though the mechanism (metal-carbene formation from
MTO) has not been finally elucidated, the multifarious applications of the catalyst are already convincing. Still more
important is the possibility of a designed catalyst optimization by variation of the alkyl groups on the metal. The activity and stability of the “classical” olefin metathesis catalyst
W-6940 Weinheim, 1991
0570-0833/9i~l2f2-1637$3.50+ ,2510
Table 2. MTO-catalyzed ring-opening polymerization of norbornene (25 "C,chlorobenzene, [Re]:[norbornene] = 1500).
Polymer yield
cis-Proportion of bonds [a]
I %I
[gmol - '1
[g mol
800 000
[a] Determination by I3C NMR. [b] Referred to polystyrene standard
metals, molybdenum and tungsten, could also be optimized
in this way. Moreover, catalytic properties are expected
for the organic oxides of the neighboring element, osmium.
Simple compounds such as O=Os(CH,), are known.['31
Experimental Procedure
MTO as heterogeneous catalyst: MTO ( l a , 1.25 g, 5.0 mmol) was dissolved in
50 mL of CH,CI, and added to a well-stirred suspension of the carrier material
(161, 13Og in 500 mL of CH,CI,).
Metathesis of I-hexene: CH,CI, (24.5 mL) was added to 1% of this contact
suspension (3 wt % Re) in a lOOmL round-bottomed flask fitted with a nitrogen
inlet and a reflux condenser. The mixture was treated with I-hexene (5mL,
40 mmo1;'Re:olefin = 1:800). The system was kept under slight positive pressure of dry nitrogen by means of a mercury check valve. (If the reaction was
carried out under reflux to drive off the evolving ethylene, 93 % of the initial
olefin was converted after 30 min.) After fractional microdistillation of the
reaction mixture 5-decene was isolated as cis/trans mixture. Yield: 2.0 g (77 %).
Cometathesis of methyl oleate and ethylene: CH,Cl, (35 mL) and methyl oleate
(1.7 mL, 5 mmol) were added to 1% of the contact suspension (Re: olefin =
1:lOO) in a l0OOmL laboratory glass autoclave and pressurized with 7 bar
ethylene. After 2 h at room temperature 27% of the starting material had
reacted (see Table 1).
Norbornene polymerization: To a solution of MTO (6.3 mg, 2.5 x 10- mmol),
chlorobenzene (3 mL), and CH,AICI, (100 pL of a 1 M solution in n-hexane)
was added a solution of norbornene (1.2 g, 12.5 mmol) in 10 mL of chlorobenzene (Re:Al:olefin = 1:4:500). No starting material could be detected after
30 min. The reaction was stopped with 20 mL of methanol. A white polymer
precipitated and was purified by dissolution in CHCI, and reprecipitation with
CH,OH. Yield: 1.1 g, 94%.
Received: July 19, 1991 [24805 IE]
German version: Angew. Chem. 103 (1991) 1704
CAS Registry numbers:
Starting olefins of Table 2: a, 109-68-2;b, 592-41-6; c, 1119-51-3;d, 2695-47-8;
e. 762-72-1, f, 18146-00-4;g, 557-31-3; h, 6140-80-3; i, 106-95-6;k, 25291-17-2;
I, 80793-18-6; m, 27854-28-6; n. 68480-06-8; 0, 2462-84-2. 1 a, 70197-13-6;
AI,O,. 1344-28-1; SO , , 7631-86-9; CH,=CH,, 74-85-1; MeAICI,. 917-65-7;
Me,AICI. 1184-58-3; EtAICI,. 563-43-9; Et,AICI, 96-10-6; NH,ReO,, 1359865-7; SnMe,, 594-21-4; (Z)-(BuCHS,, 7433-78-5; (E)-(BuCHS, , 7433-56-9;
(MeCH , 107-01-7;(EtCH ,592-47-2 ;[Br(CH,),CH 1 , 100960-98-3;[Br(CH,),CH-),, 137040-97-2;(TMSCH,CH+,, 3528-12-9; (TMSOCH,CH+,,
61549-43-7; (EtOCH,CH+,.
7250-85-3; (iPrOCH,CH+,, 88482-36-4;
(BrCH,CH+,, 6974-12-5; (C6F,,CHS2, 56523-43-4; (C,F,,CH,CH+,,
137091-62-4; [C6F1,(CH2),CH),.
137040-98-3; [EtCOO(CH,)8CH+,.
137040-99-4; [Me(CH,),CHf , 5557-31-3 ; [MeO,C(CH,),CH), , 13481-975; norbornene, 498-66-8; norbornene polymer, 25038-76-0; cyclopentane, 28792-3.
[I] a) Review: W. A. Hernnann, Angew. Chem. 100 (1988) 1297; Angew.
Chem. Int. Ed. Engl. 27 (1988) 1269; b) synthesis: W. A. Herrmann,
J. G. Kuchler, G. Weichselbaumer, E. Herdtweck, P. Kiprof, J. Organomet. Chem. 372 (1989) 351.
[2] a) J. C. Mol, J. A. Moulijn (Catalytic Metathesis of Alkenes) in M. Boudart
(Eds.): Catalysis-Science and Technology, Vol. 8 , Springer, Berlin 1987,
p. 69ff. b) K. J. Ivin: Olefin Metathesis, Academic Press, New York 1983.
[3] Industrial applications: a) R. Streck, Chem.-Ztg. 99 (1975) 397; b)
S. Warwel, Erdol Erdgas Kohle 103 (1987) 238; c) R. F.Ohm,
CHEMTECH 10 (1980) 183; d) J. C. Mol, ibid. 13 (1983) 250; e)
W. A. Herrmann, Kontakte (Darmstadt) 3 (1991) 29-52.
Verlagsgesellschaft mbH. W-6940 Weinheim. 1991
[4] W. A. Herrmann, J. G. Kuchler, J. K. Felixberger, E. Herdtweck,
W. Wagner, Angew. Chem. 100 (1988) 420; Angew. Chem. Int. Ed. Engl. 27
(1988) 394.
[5] W. A. Herrmann, W. Wagner, U. Volkhardt, DOS-DE 3940196 (December 12,1989/June 13,1990). Hoechst AG; DOS-DE 3902357 (January 27,
1989/August 2,1990), Hoechst AG; DOS-DE 4009910 (October 2, 1991)
Hoechst AG.
[6] AI,O,-SO, containing 13 wt% AI,O, (grain size > I 5 pm) from Strem
Chemicals Inc., Newburyport, MA, USA, was heated for 1 h a t 550°C in
a stream of nitrogen and then doped with CH,ReO,. The catalyst must be
handled in a dry atmosphere.
[7] S. Warwel, H. Ridder, G. Hachen, Chem.-Zrg. 107 (1983) 115.
[SJ R. Buffon, A. Choplin, M. Leconte, J.-M. Basset, W. Wagner, W A. Herrmann, J. Mol. Catal., in press.
[9] a) J. Takdcs, P. Kiprof, J. Riede, W. A. Herrmann, Organometallics 9
(1990) 783; b) W A. Herrmann, P. Watzlowik, P. Kiprof, Chem. Ber. 124
(1991) 1101.
[lo] Cf. W. A. Herrmann, K. Rypdal, R. Tremmel, R. Blom, P. Kiprof, R.
Alberto. J. Behm, R. W Albach, H. Bock, B. Solouki, J. Mink, D. Lichtenberger, N. E. Gruhn, J. Am. Chem. Sor. 113 (1991) 6527.
[ I l l a) K. P. J. Williams, K. Harrison, J. Chem. SOC.
Faraday Trans. 86 (1990)
1603; b) E. D. Hardcastle. J. E. Wachs, 1 Mol. Catal. 46 (1988) 15.
[12] K. I. Ivin, J. J. Rooney. C . D. Stewart. J. Chem. SOC.Chem. Commun. 1978,
I131 W. A. Herrmann. S. J. Eder, P. Kiprof, K. Rypdal, Angew. Chem. 102
(1990) 1460; Angew. Chem. Int. Ed. Engl. 29 (1990) 1445.
Methyltrioxorhenium as Catalyst for
Olefin Oxidation**
By Wovgang A . Herrmann,* Richard W Fischer,
and Dieter W Marz
Dedicated to Professor Karl Heinz Biichel
on the occasion ofhis 60th birthday
The oxides of the neighboring elements of rhenium are
active catalysts for olefin oxidation.['] They depend, however, on different mechanisms for their activity: With hydrogen peroxide, molybdenum and tungsten oxides form "inorganic peroxides" of type L,M-OOH, which have proved to
be efficient epoxidation agents. Osmium tetroxide reacts
with olefins cis-stereoselectively-in stoichiometric and catalytic processes-to yield vicinal diols, which are formed
via structurally defined osmate esters.['**' However, no
Prof. Dr. W. A. Hernnann, R. W. Fischer, Dr. D. W. Ma n [ +]
Anorganisch-chemisches Institut der Technischen Universiet Miinchen
Lichtenbergstrasse 4, W-8046 Garching (FRG)
['I New address: PCI Polychemie GmbH
Piccardstrasse 4, W-8900 Augsburg 1 (FRG)
[**I Multiple Bonds between Main-Group Elements and Transition Metals,
Part 100, second communication. (The first and third communications
precede and follow this paper.) This work was supported by the Hoechst
AG and the Fonds der Chemischen Industrie. Part 99: W. A. Hemnann,
S. J. Eder, P. Kiprof, J. Organomet. Chem. 412 (1991) 407-414.
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 12
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