WO2013098052A2

WO2013098052A2 - Metathesis of nitrile rubbers in the presence of transition metal complex catalysts

Info

Publication number: WO2013098052A2
Application number: PCT/EP2012/074495
Authority: WO
Inventors: Christopher Ong
Original assignee: Lanxess Deutschland Gmbh
Priority date: 2011-12-28
Filing date: 2012-12-05
Publication date: 2013-07-04
Also published as: WO2013098052A3; TW201341405A

Abstract

The present invention relates to a process for the preparation of optionally hydrogenated nitrile rubber with reduced molecular weights by subjecting an optionally hydrogenated nitrile rubber to a metathesis reaction in the presence of a transition metal catalyst complex in a specific reaction mixture.

Description

Metathesis of nitrile rubbers in the presence of transition metal complex catalysts

FIELD OF THE INVENTION

The present invention relates to a process for preparing optionally hydrogenated nitrile rubber with low molecular weight by molecular weight degradation of optionally hydrogenated nitrile rubbers via a metathesis process in the presence of a transition metal complex catalyst in a specific reaction mixture.

BACKGROUND OF THE INVENTION

Nitrile rubber, also referred to as "NBR" for short, is used as starting material for producing hydrogenated nitrile rubber, referred to as "HNBR" for short. NBR and HNBR are also referreed to as (H)NBR in this application unless indicated otherwise. Nitrile rubbers are copolymers of at least one unsaturated nitrile, at least one conjugated diene and optionally further copolymerizable comonomers. HNBR is typically prepared by selective hydrogenation of NBR.

NBR and HNBR are specialty rubbers with an attractive property profile. Hydrogenated nitrile rubber in particular has very good heat resistance, excellent ozone and chemical resistance, and excellent oil resistance. Coupled with the high level of mechanical properties of the rubber (in particular the high resistance to abrasion) it is not surprising that HNBR as well as NBR have found widespread use in the automotive (seals, hoses, bearing pads) oil (stators, well head seals, valve plates), electrical (cable sheathing), mechanical engineering (wheels, rollers) and shipbuilding (pipe seals, couplings) industries, amongst others.

For a long time commercially available HNBR grades had a Mooney viscosity (ML 1+4 at 100°C) in the range from 55 to 120, which corresponds to a number average molecular weight M_n (method of determination: gel permeation chromatography (GPC) against polystyrene equivalents) in the range from about 200,000 to 700,000. The polydispersity index PDI (PDI = M_w/M_n, where M_w is the weight average molecular weight and M_n is the number average molecular weight), which gives information about the width of the molecular weight distribution, is frequently 3 or above. The residual double bond content is usually in the range from 0 to 18% (determined by IR spectroscopy). A nitrile rubber is typically considered to be and called "fully hydrogenated" in literature, if the residual double bond content is at maximum 0,9 %.

The processability of (H)NBR is subject to severe restrictions as a result of the relatively high Mooney viscosity. For many applications, it would be desirable to have (H)NBR grades which have a lower molecular weight and thus a lower Mooney viscosity. This would decisively improve the processability. In particular for HNBR numerous attempts have been made in the past to to reduce the molecular weight of the polymer, i.e. to shorten the chain length of HNBR by degradation. For example, the molecular weight can be decreased by thermomechanical treatment (mastication, i.e. mechanical breakdown), e.g. on a roll mill or in a screw apparatus (EP-A-0 419 952). However, this thermomechanical degradation has the disadvantage that functional groups such as hydroxyl, keto, carboxyl and ester groups are incorporated into the molecule as a result of partial oxidation and, in addition, the microstructure of the polymer is substantially altered. This results in disadvantageous changes in the properties of the polymer. In addition, these types of approaches, by their very nature, produce polymers having a broad molecular weight distribution.

HNBR having a low Mooney viscosity and improved processability, but which has the same microstructure as those rubbers which are currently available, is difficult to manufacture using current technologies. The hydrogenation of NBR to produce HNBR results in an increase in the Mooney viscosity of the raw polymer. This so called Mooney Increase Ratio ("MIR") is generally around 2, depending upon the polymer grade, hydrogenation level and nature of the feedstock.

Furthermore, limitations associated with the production of NBR itself dictate the low viscosity range for the HNBR feedstock.

In WO-A-02/100905, WO-A-02/100941, and WO-A-2003/002613 a low-Mooney HNBR is disclosed as well as a method for producing said low-Mooney HNBR. Such method comprises degradation of a starting nitrile rubber by olefin metathesis and subsequent hydrogenation. The starting nitrile rubber is reacted in a first step in the optional presence of a coolefin and a specific catalyst based on osmium, ruthenium, molybdenum or tungsten complexes and hydrogenated in a second step. The hydrogenated nitrile rubbers obtained typically have a weight average molecular weight (Mw) in the range from 30,000 to 250,000, a Mooney viscosity (ML 1+4 at 100°C) in the range from 3 to 50 and a polydispersity index, PDI, of less than 2.5.

Metathesis catalysts are known, inter alia, from WO-A-96/04289 and WO-A-97/06185. They have the following in-principle structure:

where M is osmium or ruthenium, R and Ri are organic radicals having a wide range of structural variation, X and Xi are anionic ligands and L and Li are uncharged electron donors. The customary term "anionic ligands" is used in the literature regarding such metathesis catalysts to describe ligands which are always negatively charged with a closed electron shell when regarded separately from the metal centre.

The metathesis reaction is typically carried out in a suitable solvent which does not deactivate the catalyst used and also does not adversely affect the reaction in any other way. Preferred solvents include e.g. dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane and cyclohexane. One of the preferred solvents is chlorobenzene.

Considerable academic attention has recently been given to ionic liquids in general. So far ionic liquids have been applied in various general olefin processes such as olefin hydrogenation (Dyson et al., J. of Organometallic Chem., 2005, 690, 3552), hydroformylation (Esterhuysen et al, J. of the Chemical Society - Dalton Transactions, 2002, 1132), carbonylation (Kollar et al., Chem.

Communications, 2000, 1695), carboxylation (Arai et al., Catalysis Communications, 2004, 5,

83) and as new solutions for Transition Metal Catalysis (Wasserscheid et al., Angew. Chem. Int. Ed., 2000, 39, 3772). In BR 9802101 it is further described to hydrogenate unsaturated polymers by the reaction of gaseous hydrogen in the presence of catalysts based on transition metals dissolved in ionic liquids.

The use of ionic liquids has further been described for specific metathesis reactions performed with low-molecular weight olefins:

In Tetrahedron Letters, 2006, 47, 2921et al. it is disclosed that cross metathesis of low molecular weight substrates such as styrene may be performed in ionic liquids utilizing supported Ru catalyst systems.

In Chem Comm. 2004, 2282 ring-closing metathesis in a biphasic ionic liquid/toluene medium is decribed in which supported Ru catalysts were utilized for the metathesis of substituted dienes.

In Organic Letters, 2001, 3(23), p. 3785 the efficiency of a Grubbs type metathesis catalyst to be recycled several times from an ionic liquid media reaction following the ring-closing metathesis of a complex diene substrate is investigated.

In addition the ring-opening metathesis polymerization (ROMP) of functional norbornenes in the presence of an ionic liquid and a ruthenium based catalyst system is described in Macromolecules, 2006, 39, 7821. Similarly the utilization of ionic liquids in the field of metathesis has been described in several patents and patent applications:

The utilization of ionic liquids and metathesis for preparing cyclic compounds with Ru based olefin metathesis catalysts in the presence of ionic liquids is known from EP-A-1 035 093.

US 2006/0079704 A describes the benefits of using ionic liquids for the metathesis of unsaturated fat (i.e. oleic sunflower seed oil & oleic rapeseed oil) and ethylene to produce an olefinic fraction and a composition of monoalcohol or polyol esters.

US 2004/0026666 A teaches of the utilization of ionic liquids as solvents in catalyzed organic reactions such as the telomerisation of conjugated olefins, olefin polymerizations & oligomerisations, the hydrogenation of olefins and olefin metathesis. In US-A-6,380,420 it is described to produce fatty acid nitriles and fatty amines by cross- metathesis of normal alpha olefins and acrylonitrile to form an intermediate fatty acid nitrile. The metathesis reaction is carried out in a biphasic solution of an ionic liquid and a solvent (hexane) utilizing a molybdenum catalyst. Additionally US-A-5,675,051 investigated the benefits of performing olefin metathesis reactions in the presence of a tungsten and/or molybdenum catalyst dissolved in an ionic liquid.

The metathesis reaction of HNBR and NBR is still encountered with substantial drawback as outlined above. The reaction is typically carried out in organic solvents. In order to achieve the necessary high dilution large reaction volumes of such organic solvents are required. This, of course, limits the maximum space-time yields. Separating off the products after the reaction is complete requires time-consuming separation operations such as chromatography and usually leads to irreversible deactivation of the catalyst used. Hence, such metathesis reactions of HNBR in organic solvents do not yet satisfy all needs and expectations with regard to the space-time yields, the reaction mixture's work-up as well as the catalyst recovery. Therefore there is room for improvement in this regard.

SUMMARY OF THE INVENTION

The present invention relates to a process for reducing the molecular weight of an optionally hydrogenated nitrile rubbers by subjecting the optionally hydrogenated nitrile rubber to a metathesis reaction in the presence of at least one ionic liquid and a transition metal complex catalyst having at least one ligand bound in a carbene-like fashion to the center metal of the complex catalyst.

DETAILED DESCRIPTION OF THE INVENTION

It has surprisingly been found that the presence of ionic liquids in the metathesis reaction of optionally hydrogenated nitrile rubbers leads to an increase in the space-time yields and the amount of catalyst to be used may be reduced. Furtheron the separation between the catalyst and the optionally hydrogenated nitrile rubber with the reduced molecular weight after the end of the reaction is facilitated which makes it possible to reuse the catalytic system.

For the purposes of the present patent application and invention, all the definitions of radicals, parameters or explanations given above or below in general terms or in preferred ranges can be combined with one another in any way, i.e. including combinations of the respective ranges and preferred ranges.

The term "substituted" used for the purposes of the present patent application in respect of the metathesis catalyst or the salt of the general formula (I) means that a hydrogen atom on an indicated radical or atom has been replaced by one of the groups indicated in each case, with the proviso that the valence of the atom indicated is not exceeded and the substitution leads to a stable compound.

The presence of at least one ionic liquid represents an important element of the present invention.

Ionic liquids to be used in the process of the invention are salts or salt mixtures which are liquid in a temperature range from -20°C to 300°C, preferably from 0°C to 150°C, and particularly preferably from 20°C to 100°C.

Ionic liquids are typically defined through both, their cationic and their anionic portions. For the present invention the ionic liquid can represent, but is not restricted to compounds on the basis of quaternary ammonium cations, quaternary phosphonium cations, optionally substituted pyridinium cations, optionally substituted imidazolium cations, optionally substituted pyrazolium cations, and optionally substituted pyrimidinium cations. Preferably the process according to the present invention is performed using at least one ionic liquid which is selected from the group consisting of the ionic liquids having the general formulae (l) to (5)

(1 ) (3)

(5)

wherein

A^n" shall mean an anion selected from the group consisting of hexafluorophosphate (PF₆ ^~), nitrate (N0₃)^~, halides, preferably fluoride, chloride, bromide or iodide, sulfates, sulfonates, aluminates, carboxylates, phosphates and borates, with n meaning 1 , 2 or 3 depending on the negative charge of the aforementioned anions and (1/n) therefore representing 1 for a one time negatively charged anion, 1/2 for a two times negatively charged anion and 1/3 for a three times negatively charged anion,

X is nitrogen or phosphorous,

R¹, R², R³, R⁴, R⁵ and R⁶ are identical or different and represent hydrogen, halide, alkoxy, alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, and

Z¹, Z², Z³ are identical or different and represent carbon (C) or nitrogen (N), under the first proviso, that at least one of Z¹, Z², and Z³ is nitrogen and under the second proviso that when any of Z¹, Z², Z³ are nitrogen the attached R¹, R², or R³group is null.

Preferably the process according to the present invention is performed in the presence of at least one ionic liquid pursuant to one of the aforementioned general formulae (l)-(5) wherein n is 1 and A- represents PF₆-, N0₃ ^", F-, CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄ ^", and B(R⁷)₄ ^", where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, more preferably phenyl, substituted aryl, or alkoxy. In one more preferred embodiment the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (1) wherein n is 1 and

A- represents PF₆ ^" , N0₃ ^", , CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄ ^~, and B(R⁷)₄ ^", where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,

X is nitrogen or phosphorus and

R¹, R², R³, and R⁴ are identical or different and shall mean alkoxy, alkyl or aryl each having 1-25 carbon atoms. In a further more preferred embodiment the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (2) wherein n is 1 and

A- represents PF₆ ^" , N0₃ , F, CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄ ^", and B(R⁷)₄ ^", where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,

R¹, R², R³, R⁴, R⁵ and R⁶ are identical or different and shall mean alkoxy, alkyl or aryl each having

1-25 carbon atoms.

In a further more preferred embodiment the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (3) wherein n is 1 and

A- represents PF₆ ^" , N0₃ , F, CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄\ and B(R⁷)₄ ^", where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, even more preferably phenyl, substituted aryl, or alkoxy,

R¹, R², R³, R⁴, and R⁵ are identical or different and shall mean alkoxy, alkyl or aryl each having 1-

25 carbon atoms.

More preferably the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (4) wherein n is 1 and

A- represents PF₆ ^" , N0₃ , F, CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄\ and B(R⁷)₄ ^", where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, or alkoxy,

R¹, R², R³, R⁴, and R⁵ are identical or different and shall mean alkoxy, alkyl or aryl each having

1-25 carbon atoms.

More preferably the process according to the present invention is performed in the presence of at least one ionic liquid of general formula (5) wherein n is 1 and represents PF₆\ N0₃ , F\ CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^", BF₄ ^", and B(R⁷)₄ ^~, where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, preferably phenyl, substituted aryl, or alkoxy,

z¹, z², z •^:3 are identical or different and represent carbon (C) or nitrogen (N), under the first proviso, that at least one of Z¹, Z², and Z³ is nitrogen and under the second proviso that when any of Z 1 , Z2 , Z 3 are nitrogen the attached R 1 , R2 , or R 3 group is null, and R¹, R², R³, R⁴, R⁵ and R⁶ are identical or different alkoxy, alkyl or aryl radicals each having 1 -25 carbon atoms.

In a specific embodiment the process of the present invention is performed using at least one ionic liquid selected from the group consisting of l-ethyl-3-methyl-pyridinium ethylsulfate, l-ethyl-3- methyl-imidazolium ethylsulfate, l-methyl-3-butylimidazolium chloride, l-methyl-3-ethylimidazo- lium chloride, N-butylpyridinium chloride, tetrabutylphosphonium chloride, ammonium hexa- fluorophosphate, ammonium tetrafluoroborate, ammonium tosylate, ammonium hydrogen sulphate, pyridinium hexafluorophosphate, l-methyl-3 -butyl imidazolium hexafluorophosphate, pyridinium tetrafluoroborate, pyridinium hydrogen sulphate, N-butylpyridinium hexafluorophosphate and combinations of two or more of the aforementioned ionic liquids.

CATALYSTS:

In the process of the invention, the catalysts or catalyst precursors used are transition metal complex carbenes or transition metal complex ompounds which form transition metal carbenes under the reaction conditions or transition metal salts in combination with an alkylating agent. These catalysts can be either ionic or nonionic.

The process of the present invention may be performed in the presence of a catalysts having the general formula (A),

where

M is osmium or ruthenium,

X¹ and X² are identical or different and are two ligands, preferably anionic ligands,

L are identical or different ligands, preferably uncharged electron donors,

R are identical or different and are each hydrogen, alkyl, preferably Ci-C₃o-alkyl, cycloalkyl, preferably C₃-C2o-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, alkynyl, preferably C2-C2o-alkynyl, aryl, preferably C6-C24-aryl, carboxylate, preferably C₁-C₂₀- carboxylate, alkoxy, preferably Ci-C2o-alkoxy, alkenyloxy, preferably C2-C20- alkenyloxy, alkynyloxy, preferably C2-C2o-alkynyloxy, aryloxy, preferably C6-C24- aryloxy, alkoxycarbonyl, preferably C2-C2o-alkoxycarbonyl, alkylamino, preferably Ci-C3o-alkylamino, alkylthio, preferably Ci-C3o-alkylthio, arylthio, preferably C6-C24- arylthio, alkylsulphonyl, preferably Ci-C2o-alkylsulphonyl, or alkylsulphinyl, preferably Ci-C2o-alkylsulphinyl, where these groups may in each case optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moities or, as an alternative, the two groups R together with the common carbon atom to which they are bound are bridged to form a cyclic structure which can be aliphatic or aromatic in nature, may be substituted and may contain one or more heteroatoms.

Various representatives of the catalysts of the formula (A) are known in principle, e.g. from WO-A-96/04289 and WO-A-97/06185. In preferred catalysts of the general formula (A), one group R is hydrogen and the other group R is

Ci-C2o-alkyl, C3-Cio-cycloalkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, C6-C24-aryl, Ci-C2o-carboxylate, Ci-C2o-alkoxy, C2-C2o-alkenyloxy, C2-C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C3o-alkylamino, Ci-C3o-alkylthio, C6-C24-arylthio, Ci-C2o-alkylsulphonyl or C1-C20- alkylsulphinyl, where these moiety may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.

In the catalysts of the general formula (A), X¹ and X² are identical or different and are two ligands, preferably anionic ligands. X¹ and X² can be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched

Ci-C3o-alkyl, C6-C24-aryl, Ci-C2o-alkoxy, C6-C24-aryloxy, C3-C2o-alkyldiketonate C6-C24- aryldiketonate, Ci-C2o-carboxylate, Ci-C2o-alkylsulphonate, C6-C24-arylsulphonate, C1-C20- alkylthiol, C6-C24-arylthiol, Ci-C2o-alkylsulphonyl or Ci-C2o-alkylsulphinyl. X¹ and X² can also be substituted by one or more further groups, for example by halogen, preferably fluorine, Ci-Cio-alkyl, Ci-Cio-alkoxy or C6-C24-aryl, where these groups, too, may once again be substituted by one or more substituents selected from the group consisting of halogen, preferably fluorine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl. In a preferred embodiment, X¹ and X² are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, Ci-C₅-carboxylate, Ci-C₅-alkyl, phenoxy, C1-C5- alkoxy, Ci-C₅-alkylthiol, C6-C24-arylthiol, C6-C24-aryl or Ci-C₅-alkylsulphonate. In a particularly preferred embodiment, X¹ and X² are identical and are each halogen, in particular chlorine, CF₃COO, CH₃COO, CFH₂COO, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH₃-C₆H₄-S0₃), mesylate (CH₃-S0₃) or CF₃ S 0₃ (trifluoromethanesulphonate) .

In the general formula (A), the symbols L represent identical or different ligands and are preferably uncharged electron donating ligand.

The two ligands L can, for example, be, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine (the latter two also being jointly referred to as "Im" ligand(s)).

The term "phosphinite" includes, for example, phenyl diphenylphosphinite, cyclohexyl dicyclohexylphosphinite, isopropyl diisopropylphosphinite and methyl diphenylphosphinite.

The term "phosphite" includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert- butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite. The term "stibine" includes, for example, triphenylstibine, tricyclohexylstibine and trimethylstibine.

The term "sulfonate" includes, for example, trifluoromethanesulphonate, tosylate and mesylate.

The term "sulfoxide" includes, for example, (CH₃)₂S(=0) and (C₆H₅)₂S=0.

The term "thioether" includes, for example, CH₃SCH₃, C₆H₅SCH₃, CH₃OCH₂CH₂SCH₃ and tetrahydrothiophene.

For the purposes of the present application, the term "pyridine" is used as a collective term for all nitrogen-containing ligands as are mentioned by, for example, Grubbs in WO-A-03/011455.

Examples are: pyridine, picolines (including α-, β- and γ-picoline), lutidines (including 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine), collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4-(dimethylamino)pyridine, chloropyridines, bromopyridines, nitropyridines, quinoline, pyrimidine, pyrrole, imidazole and phenylimidazole.

In a preferred embodiment catalysts of general formula (A) are used in which one or both of ligands L represent an imidazoline or imidazolidine ligand (also jointly referred to as "Im"- ligand in this application unless indicated otherwise), having a structure of general formulae (Ila) or (lib), wherein the meaning of L can be identical or different in case both ligands L have a structure according to (Ila) or

(Ila) (Mb)

where

R⁸' R⁹, R¹⁰ and R¹¹ are identical or different and represent hydrogen, straight-chain or branched Cp C₃₀-alkyl, C₃-C₂o-cycloalkyl, C₂-C₂o-alkenyl, C₂-C₂o-alkynyl, C₆-C₂₄-aryl, C₇-C₂₅-alkaryl, C₂-C₂₀ heteroaryl, C₂-C₂o heterocyclyl, Ci-C₂o-alkoxy, C₂-C₂o-alkenyloxy, C₂-C₂o-alkynyloxy, C6-C₂o- aryloxy, C₂-C₂₀-alkoxycarbonyl, C_rC₂₀-alkylthio, C₆-C₂₀-arylthio, -Si(R)₃, -0-Si(R)₃, -0-C(=0)R, C(=0)R, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂, -S0₂N(R)₂ , -S(=0)R, -S(=0)₂R, -0-S(=0)₂R, halogen, nitro or cyano, wherein in all above occurences relating to the meanings of R⁸' R⁹, R¹⁰ and R¹¹ the group R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl. If appropriate, one or more of R⁸, R⁹, R¹⁰, and R¹¹ can independently of one another, be substituted by one or more substituents, preferably straight-chain or branched Ci-Cio-alkyl, C₃-Cg-cycloalkyl, CpCio-alkoxy or C6-C₂4-aryl, C₂-C₂o heteroaryl, C₂-C₂o heterocyclic, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, where these abovementioned substituents, to the extent chemically possible, may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl. Merely in the interest of clarity, it may be added that the structures of the imidazoline and imidazolidine ligand depicted in the general formulae (Ila) and (lib) in the present patent application are equivalent to the structures (Ila') and (lib') which are frequently also found in the literature for this imidazoline and imidazolidine ligand, respectively, and emphasize the carbene character of the imidazoline and imidazolidine. This applies analogously to the associated preferred structures (Illa)-(IIIu) depicted below.

In a preferred embodiment of the catalysts of the general formula (A),

R⁸ and R⁹ are each identical or different and represent hydrogen, C6-C24-aryl, straight-chain or branched Ci-Cio-alkyl, or form a cycloalkyl or aryl structure together with the carbon atoms to which they are bound.

More preferably

R⁸ and R⁹ are identical and are selected from the group consisting of hydrogen, methyl, propyl, butyl and phenyl.

The preferred and more preferred meanings of R⁸ and R⁹ may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched Ci-Cio-alkyl or Cp Cio-alkoxy, C3-Cg-cycloalkyl, C6-C24-aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, C1-C5- alkyl, Ci-C₅-alkoxy and phenyl.

R¹⁰ and R¹¹ are identical or different and preferably represent straight-chain or branched C1-C10- alkyl, C3-Cio-cycloalkyl, C6-C24-aryl, particularly preferably phenyl, Ci-Cur alkylsulfonate, C6-Cio-arylsulfonate.

More preferably

R¹⁰ and R¹¹ are identical and are selected from the group consisting of i-propyl, neopentyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, or 2,4,6- trimethylphenyl.

The preferred meanings of R¹⁰ and R¹¹ may be substituted by one or more further substituents selected from the group consisting of straight-chain or branched Ci-Cio-alkyl or Ci-Cio-alkoxy, C3- Cg-cycloalkyl, C6-C24-aryl, and a functional group selected from the group consisting of OH, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherin all these substituents may in turn be substituted by one or more substituents, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl.

Particularly preferred are catalysts of general formula (A) in which one or both of ligands L represent imidazoline and imidazolidine ligands having the structures (Ilia) to (IIIu), where "Ph" means in each case phenyl, "Bu" means butyl, "Mes" represents in each case 2,4,6-trimethylphenyl, "Dipp" means in all cases 2,6-diisopropylphenyl and "Dimp" means 2,6-dimethylphenyl, and wherein the meaning of L can be identical or different in case both ligands L in general formula (A) have a structure according to (Ilia) to (IIIu),

(Ilia) (1Mb) (NIC)

Bu Bu Bu^ ^Bu

\^ ^

I— I

Dipp J Dipp Dipp Dipp Dipp - - ^oipp

(lllm) (Illn

(Nik)

Ph

I I [=1

Dimp "Dimp Dimp' "Dimp Dimp "Dimp

(lllp) (ll lq) (ll lr)

(Ills) (lilt) (l llu) In a further preferred embodiment of catalyst (A) one or both of the ligands L may have the meaning of general formulae (lie) or (lid), wherein the meaning of L can be identical or different in case to (lie) or (lid),

(l ie) (l id)

wherein

R⁸, R⁹ and R¹⁰ may have all general, preferred, more preferred and most preferred meanings as defined above in relation to general formulae (Ila) and (lib), and

R¹⁵, R¹⁶ and R¹⁷ are identical or different and may represent alkyl, cycloalkyl, alkoxy, aryl, aryloxy, or a heterocyclic group.

In general formulae (lie) and (lid) R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶ and R¹⁷ may also be substituted by one or more further, identical or different substituents selected from the group consisting of straight-chain or branched Ci-C₅-alkyl, in particular methyl, Ci-C₅-alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulphide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.

In a more preferred embodiment the ligands L has the general formula (lid) wherein

R¹⁵, R¹⁶ and R¹⁷ are identical or different, even more preferably identical, and can represent d-

C₂o alkyl, C₃-C₈-cycloalkyl, C1-C20 alkoxy, C₆-C₂o aryl, C₆-C₂o aryloxy, C₂-C₂o heteroaryl or a C₂-C₂o heterocyclic group.

In an even more preferred embodiment the ligand L has the general formula (lid) wherein

R¹⁵, R¹⁶ and R¹⁷ are identical and each selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2- methylbutyl, 3 -methylbutyl, neopentyl, 1 -ethylpropyl, n-hexyl, neophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, tolyl, 2,6-dimethylphenyl, and trifluoromethyl.

In case one or both of the ligand L possess general formula (lid) it most preferably represents PPh₃, P(p-Tol)₃, P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃, P(C₆H₄-S0₃Na)₃, P(CH₂C₆H4-S0₃Na)3, P(isopropyl)₃, P(CHCH3(CH₂CH₃))3, P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃ or P(neophenyl)₃.

The following catalysts with structures (IV) (Grubbs I catalyst) and (V) (Grubbs II catalyst) shall also be covered b component (1), where Cy is cyclohexyl.

The process of the present invention may be performed in the presence of a catalysts having the general formula (Al),

where

X¹, X² and L can have the same general, preferred and particularly preferred meanings as in the general formula (A),

n is 0, 1 or 2,

m is 0, 1 , 2, 3 or 4 and

R' are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals which may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl.

A further catalyst of general formula (Al) is the catalyst of the formula (VI) below, where Mes is in each case 2,4,6-trimethylphenyl and Ph is phenyl.

This catalyst which is also referred to in the literature as "Nolan catalyst" is known, for example, from WO-A-2004/112951.

Further catalysts to be covered by component (1) are the catalysts of the general formula (B),

where

M is ruthenium or osmium,

X¹ and X² are identical or different and are anionic ligands,

R" are identical or different and are organic moieties,

Im is a substituted or unsubstituted imidazoline or imidazolidine ligand and

An is an anion.

The catalysts of the general formula (B) are known in principle (see, for example, Angew. Chem. Int. Ed. 2004, 43, 6161-6165).

X¹ and X² in the general formula (B) can have the same general, preferred and particularly preferred meanings as in the formula (A). The imidazoline or imidazolidine ligand usually has a structure of the general formulae (Ila) or

(lib) which have been mentioned above for the catalyst of general formula (A) and can have all the structures mentioned there as preferred, in particular those of the formulae (Illa)-(IIIu).

In general formula (B) R" are identical or different and are each a straight-chain or branched Cp C3o-alkyl, C₅-C3o-cycloalkyl or aryl, where the Ci-C3o-alkyl moiety may be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen. Aryl is an aromatic radical having from 6 to 24 skeletal carbon atoms. As preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic moieties having from 6 to 10 skeletal carbon atoms, mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

Preference is given to R" in the general formula (B) being identical and each being phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or mesityl.

Further catalysts to be covered by component (1) are the catalysts of the general formula (C),

where

M is ruthenium or osmium,

R¹³ and are each, independently of one another, hydrogen, Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, C6-C24-aryl, Ci-C2o-carboxylate, Ci-C2o-alkoxy, C2-C2o-alkenyloxy, C2-C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C2o-alkylthio, Ci-C2o-alkylsulphonyl or Ci-C2o-alkylsulphinyl,

X³ is an anionic ligand,

is an uncharged π-bonded ligand which may either be monocyclic or polycyclic, is a ligand selected from the group consisting of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines,

Y- is a noncoordinating anion and

n is 0, 1, 2, 3, 4 or 5.

The process of the present invention may be performed in the presence of a catalysts having the general formula (D), D ^{1 9}

^ M=C=C (D)

X^{l /} V

where

M is ruthenium or osmium,

X¹ and X² are identical or different and are anionic ligands which can have all meanings of

X¹ and X² mentioned in the general formulae (A) and (B),

the symbols L represent identical or different ligands which can have all general and preferred meanings of L mentioned in the general formulae (A) and (B),

R¹⁹ and R²⁰ are identical or different and are each hydrogen or substituted or unsubstituted alkyl.

The process of the present invention may be performed in the presence of a catalysts having the general formulae (E), (F) and (G)

(E) (F) (G)

where

M is osmium or ruthenium,

L is a ligand, preferably an uncharged electron donor,

Z¹ and Z² are identical or different and are uncharged electron donors,

R²¹ and R²² are each, independently of one another, hydrogen alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulphonyl or alkylsulphinyl which are in each case substituted by one or more substituents selected from among alkyl, halogen, alkoxy, aryl or heteroaryl.

The catalysts of the general formulae (E), (F), and (G) are known in principle, e.g. from WO 2003/011455 Al, WO 2003/087167 A2, Organometallics 2001, 20, 5314 and Angew. Chem. Int. Ed. 2002, 41, 4038. The catalysts are commercially available or can be synthesized by the preparative methods indicated in the abovementioned literature references. In the catalysts of the general formulae (E), (F), and (G) can be used in which Z¹ and Z² are identical or different and are uncharged electron donors. These ligands are usually weakly coordinating. The ligands are typically optionally substituted heterocyclic groups. These can be five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or

5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably CpCio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C6-C24-aryl, or heteroaryl, preferably C₅-C23-heteroaryl, radicals which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl.

Examples of Z¹ and Z² encompass nitrogen-containing heterocycles such as pyridines, pyridazines, bipyridines, pyrimidines, pyrazines, pyrazolidines, pyrrolidines, piperazines, indazoles, quino lines, purines, acridines, bisimidazoles, picolylimines, imidazolines, imidazolidines and pyrroles.

Z¹ and Z² can also be bridged to one another to form a cyclic structure. In this case, Z¹ and Z² form a single bidentate ligand.

In the catalysts of the general formulae (E), (F), and (G) L can have the same general, preferred and particularly preferred meanings as L in the general formula (A) and (B).

In the catalysts of the general formulae (E), (F), and (G) R²¹ and R²² are identical or different and are each alkyl, preferably Ci-C3o-alkyl, particularly preferably Ci-C2o-alkyl, cycloalkyl, preferably

C3-C2o-cycloalkyl, particularly preferably C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, particularly preferably C2-Ci6-alkenyl, alkynyl, preferably C2-C2o-alkynyl, particularly preferably C2-Ci6-alkynyl, aryl, preferably C6-C24-aryl, carboxylate, preferably Ci-C2o-carboxylate, alkoxy, preferably Ci-C2o-alkoxy, alkenyloxy, preferably C2-C2o-alkenyloxy, alkynyloxy, preferably C2- C2o-alkynyloxy, aryloxy, preferably C6-C24-aryloxy, alkoxycarbonyl, preferably C2-C20- alkoxycarbonyl, alkylamino, preferably Ci-C3o-alkylamino, alkylthio, preferably Ci-C3o-alkylthio, arylthio, preferably C6-C24-arylthio, alkylsulphonyl, preferably Ci-C2o-alkylsulphonyl, or alkylsulphinyl, preferably Ci-C2o-alkylsulphinyl, where the abovementioned substituents may be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moieties. In the catalysts of the general formulae (E), (F), and (G) X¹ and X² are identical or different and can have the same general, preferred and particularly preferred meanings as indicated above for X¹ and X² in the general formula (A). The process of the present invention may be preferably performed in the presence of a catalyst according to general formulae (E), (F), and (G) in which

M is ruthenium,

X¹ and X² are both halogen, in particular chlorine,

R¹ and R² are identical or different and are five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all the abovementioned groups may in each case be substituted by one or more moieties selected from the group consisting of alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably CpCio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably

C6-C24-aryl, or heteroaryl, preferably C₅-C23-heteroaryl,

Z¹ and Z² are identical or different and five- or six-membered monocyclic groups having from 1 to 4, preferably from 1 to 3 and particularly preferably 1 or 2, heteroatoms or bicyclic or polycyclic structures made up of 2, 3, 4 or 5 five- or six-membered monocyclic groups of this type, where all these abovementioned groups may in each case optionally be substituted by one or more alkyl, preferably Ci-Cio-alkyl, cycloalkyl, preferably C3-Cg-cycloalkyl, alkoxy, preferably CpCio-alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C6-C24-aryl, or heteroaryl, preferably C₅-C23-heteroaryl, radicals which may in turn each be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl, R²¹ and R²² are identical or different and are each Ci-C3o-alkyl C3-C2o-cycloalkyl, C2-C20- alkenyl, C2-C2o-alkynyl, C6-C24-aryl, Ci-C2o-carboxylate, Ci-C2o-alkoxy, C2-C20- alkenyloxy, C2-C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, C1-C30- alkylamino, Ci-C3o-alkylthio, C6-C24-arylthio, Ci-C2o-alkylsulphonyl, C1-C20- alkylsulphinyl, and

L has a structure of the above-described general formula (Ila) or (lib), in particular one of the formulae (Ilia) to (IIIu). A further preferred catalyst has the structure (XIX),

where R and R are identical or different and are each halogen, straight-chain or branched Cp C2o-alkyl, Ci-C2o-heteroalkyl, CpCio-haloalkyl, Ci-Cio-alkoxy, C6-C24-aryl, preferably bromine, phenyl, formyl, nitro, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, dialkylamino, trialkylsilyl or trialkoxysilyl.

The abovementioned meanings for R²³ and R²⁴ C_rC₂o-alkyl, C_rC₂o-heteroalkyl, C_rCi₀-haloalkyl, Ci-Cio-alkoxy, C6-C24-aryl, preferably phenyl, formyl, nitro, a nitrogen heterocycle, preferably pyridine, piperidine or pyrazine, carboxy, alkylcarbonyl, halocarbonyl, carbamoyl, thiocarbamoyl, carbamido, thioformyl, amino, trialkylsilyl and trialkoxysilyl may in turn each be substituted by one or more halogen, preferably fluorine, chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy or phenyl moities.

Further preferably used catalysts have the structure (XIX a) or (XIX b), where R²³ and R²⁴ have the same meanin s as indicated in formula (XIX).

(XlXa) (XlXb)

When R²³ and R²⁴ are each bromine in formula (XlXa), the catalyst is referred to in the literature as the "Grubbs III catalyst".

Further preferably used catalysts which come under general formulae (E), (F), and (G) have the structural formulae (XX)-(XXXII), where Mes is in each case 2,4,6-trimethylphenyl.

Further preferred catalysts are catalysts (N) containing the general structural element (Nl), where the carbon atom denoted by "*" is bound via one or more double bonds to the catalyst framework with a ruthenium or osmium central metal,

and where

_R25__R32 are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol,

CF₃, nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (-SO₃ ), -OSO₃ ^", -PO₃ ^" or OPO₃ ^" or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where all these moieties can each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, two directly adjacent substituents from the group consisting of R²⁵-R³² together with the ring carbons to which they are bound form a cyclic group, preferably an aromatic system, by bridging or, as an alternative, R⁸ is optionally bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst,

m is 0 or 1 and

A is oxygen, sulphur, C(R³³R³⁴), N-R³⁵, -C(R³⁶)=C(R³⁷)-, -C(R³⁶)(R³⁸)-C(R³⁷)(R³⁹)-, where

33 39 25 32

R -R are identical or different and can each have the same meanings as R -R . In the catalysts having the structural element of the general formula (Nl) the carbon atom denoted by "*" is bound via one or more double bonds to the catalyst framework. If the carbon atom denoted by "*" is bound via two or more double bonds to the catalyst framework, these double bonds can be cumulated or conjugated.

Such catalysts (N) have been described in US-A-2009/0076226, which also discloses their preparation.

The catalysts (N) having a structural element of the general formula (Nl) include, for example, cata

(N2a) (N2b)

where

M is ruthenium or osmium,

L¹ and L² are identical or different ligands, preferably uncharged electron donors, where L can alternatively also be bridged to the radical R⁸,

n is 0, 1, 2 or 3, preferably 0, 1 or 2,

n' is 1 or 2, preferably 1, and

R -R , m and A have the same meanings as in the general formula (Nl).

In the catalysts of the general formula (N2a), the structural element of the general formula (Nl) is bound via a double bond (n = 0) or via 2, 3 or 4 cumulated double bonds (in the case of n = 1 , 2 or 3) to the central metal of the complex catalyst. In the catalysts of the general formula (N2b) suitable to be used for the catalyst systems according to the invention, the structural element of the general formula (Nl) is bound via conjugated double bonds to the metal of the complex catalyst. In both cases, the carbon atom denoted by "*" as a double bond in the direction of the central metal of the complex catalyst. The catalysts of the general formulae (N2a) and (N2b) thus encompass catalysts in which the general structural elements (N3)-(N9)

are bound via the carbon atom denoted by "*" via one or more double bonds to the catalyst framework of the general formula (NlOa) or (NlOb)

(N10a) (N10b)

1 2 1 2 25 39

where X and X , L and L , n, n' and R -R have the meanings given for the general formulae (N2a) and (N2b).

The Ru- or Os-based carbene catalysts resulting thereof typically have five-fold coordination.

In the structural element of the general formula (Nl),

_R25__R32 are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF₃, nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (-SO₃ ), -OSO₃ ^", -PO₃ ^" or OPO₃ ^" or alkyl, preferably Ci-C2o-alkyl, in particular Ci-C6-alkyl, cycloalkyl , preferably C3-C20- cycloalkyl, in particular C3-Cg-cycloalkyl, alkenyl, preferably C2-C2o-alkenyl, alkynyl, preferably C2-C2o-alkynyl, aryl, preferably C6-C24-aryl, in particular phenyl, carboxylate, preferably Ci-C2o-carboxylate, alkoxy, preferably Ci-C2o-alkoxy, alkenyloxy, preferably C2-C2o-alkenyloxy, alkynyloxy, preferably C2-C2o-alkynyloxy, aryloxy, preferably C6-C24- aryloxy, alkoxycarbonyl, preferably C2-C2o-alkoxycarbonyl, alkylamino, preferably Cp C3o-alkylamino, alkylthio, preferably Ci-C3o-alkylthio, arylthio, preferably C6-C24-arylthio, alkylsulphonyl, preferably Ci-C2o-alkylsulphonyl, alkylsulphinyl, preferably C1-C20- alkylsulphinyl, dialkylamino, preferably di(Ci-C2o-alkyl)amino, alkylsilyl, preferably Cp C2o-alkylsilyl, or alkoxysilyl, preferably Ci-C2o-alkoxysilyl, where these moities can each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, in each case two directly adjacent substituents from the group consisting of R²⁵-R³² together with the ring carbons to which they are bound may also form a cyclic group, preferably an aromatic system, by bridging or, as an alternative, R⁸ is optionally bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst,

is 0 or 1 and

is oxygen, sulphur, C(R³³)(R³⁴), N-R³⁵, -C(R³⁶)=C(R³⁷)- or -C(R³⁶)(R³⁸)-C(R³⁷)(R³⁹)-, where R³³-R³⁹ are identical or different and can each have the same preferred meanings as the radicals R'-R⁸.

Ci-C6-Alkyl in the structural element of the general formula (Nl) is, for example, methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl or n-hexyl.

C3-Cg-Cycloalkyl in the structural element of the general formula (Nl) is, for example, cyclopropyl, cyclobutyl, cylopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

C6-C24-Aryl in the structural element of the general formula (Nl) comprises an aromatic radical having from 6 to 24 skeletal carbon atoms. As preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic radicals having from 6 to 10 skeletal carbon atoms, mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

X¹ and X² in the structural element of the general formula (Nl) have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula A. In the general formulae (N2a) and (N2b) and analogously in the general formulae (Nl Oa) and (Nl Ob), L¹ and L² are identical or different ligands, preferably uncharged electron donors, and can have the same general, preferred and particularly preferred meanings indicated for catalysts of the general formula A.

Further preferred catalysts of general formulae (N2a) or (N2b) have a general structural unit (Nl) in which

M is ruthenium,

X¹ and X² are both halogen,

n is 0, 1 or 2 in the general formula (N2a) or

n' is 1 in the general formula (N2b)

L¹ and L² are identical or different and have the general or preferred meanings indicated for the general formulae (N2a) and (N2b),

_R25__R32

are identical or different and have the general or preferred meanings indicated for the general formulae (N2a) and (N2b),

m is either 0 or 1 ,

and, when m = 1 ,

A is oxygen, sulphur, C(C_rCio-alkyl)₂, -C(Ci-Ci₀-alkyl)₂-C(Ci-Ci₀-alkyl)₂-, -C(Ci_Cio-

or -N(C_rCi₀-alkyl).

M is ruthenium,

X¹ and X² are both chlorine,

n is 0, 1 or 2 in the general formula (N2a) or

n' is 1 in the general formula (N2b)

L¹ is an imidazoline or imidazolidine ligand of one of the formulae (Ilia) to (IIIu),

L² is a sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine radical, an imidazolidine radical of one of the formulae (Xlla) to (Xllf) or a phosphine ligand, in particular PPh₃, P(p-

Tol)₃, P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆H₄)₃, P(p-CF₃C₆H₄)₃, P(C₆H₄-S0₃Na)₃,

P(CH₂C₆H₄-S0₃Na)₃, P(isopropyl)₃, P(CHCH₃(CH₂CH₃))₃, P(cyclopentyl)₃,

P(cyclohexyl)₃, P(neopentyl)₃ and P(neophenyl)₃,

R²⁵-R³² have the general or preferred meanings indicated for the general formulae (N2a) and

(N2b),

m is either 0 or 1

and, when m = 1 , A is oxygen, sulphur, C(C_rCio-alkyl)₂, -C(Ci-Ci₀-alkyl)₂-C(Ci-Ci₀-alkyl)₂-, -C(C_rCi₀-

or -N(C_rCio-alkyl).

When R is bridged to another ligand of the catalyst of the formula N, this results, for example for the catalysts of the general formulae (N2a) and (N2b), in the following structures of the general formulae

(N13a) (N13b)

where

Y¹ is oxygen, sulphur, N-R⁴¹ or P-R⁴¹, where R⁴¹ has the meanings indicated below, R⁴⁰ and R⁴¹ are identical or different and are each alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl which may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,

p is 0 or 1 and

Y² when p = 1 is -(CH₂)_r- where r = 1, 2 or 3, -C(=0)-CH₂-, -C(=0)-, -N=CH-, -N(H)-

C(=0)- or, as an alternative, the entire structural unit "-Y¹ (R⁴⁰)-(Y²)_P-" is (- N(R⁴⁰)=CH-CH₂-), (-N(R⁴⁰,R⁴¹)=CH-CH₂-), and

1 2 1 25 32

where M, X¹, X V, R -R , A, m and n have the same meanings as in general formulae (N2a) and (N2b).

Further preferred catalysts representing catalyst type (N) have the following structures:

In another embodiment the process of the present invention may be performed with a metathesis catalyst having the general formula (Q),

where

M is ruthenium or osmium,

X¹ and X² are identical or different ligands,

L is an electron donating ligand, which can be linked or not linked with X¹ to form a cyclic structure,

R¹ is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl and

R², R³, R⁴ and R⁵ are identical or different and are each hydrogen or an organic or inorganic substituent,

R⁶ is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, -C(=0)R, -C(=0)OR, -

C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂ , - S(=0)₂R, -S(=0)R or a group containing either a C=0 or a C=S structural element adjacent to a carbon atom which is bound to Y,

n is O or l,

wherein if n=l, then the element

Y^(E)_n

shall mean that Y and (E)_n are linked either by a single bond or by a double bond, wherein

(i) if Y and (E)_n are linked by a single bond, then

Y is oxygen (O), sulfur (S), N-R or P-R and E is CH₂ or

(ii) if Y and (E)_n are linked by a double bond, then

Y is N or P

E is CH

wherein if n=0, then

Y is oxygen (O), sulfur (S), N-R or P-R and directly linked by a single bond to the phenyl moiety depicted above in formula (Q)

and wherein in all above occurences of general formula (Q)

R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

In all the above mentioned and further down defined preferred, more preferred and most preferred embodiments of the catalysts according to general formula (Q) the alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl moieties in the respective moieties may optionally be further substituted by one or more Ci-C6-alkyl, C₅-C6-cycloalkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, halogen, aryl, preferably phenyl, heteroaryl, preferably pyridinyl, imidazolyl, or triazolyl substituents. All aforementioned substituents, in particular the alkyl, alkenyl and/or alkynyl moieties can be straight-chain or branched to the extent chemically plausible.

The catalysts of the general formula (Q) are known in principle. Representatives of this class of compounds are e.g. the catalysts described by Hoveyda et al. in US 2002/0107138 Al and Angew

Chem. Int. Ed. 2003, 42, 4592, and the catalysts described by Grela in WO-A-2004/035596, Eur.

J. Org. Chem 2003, 963-966 and Angew. Chem. Int. Ed. 2002, 41, 4038 and also in J. Org.

Chem. 2004, 69, 6894-96 and Chem. Eur. J 2004, 10, 777-784. Further representatives of this class of catalysts are the catalysts described in EP-A-1 905 777. These catalysts are either commercially available or can be prepared as described in the literature references cited.

To the extent any of the following general, preferred, more preferred or most preferred definitions of the catalyst according to general formual (Q) mention the meaning "C2-C20 heterocyclic" and "C2-C20 heteroaryl" this shall always imply that the respective heterocyclic ring or heteroaryl ring contains besides the number of carbon atoms given such an additional number of hetero atoms that a stable heterocyclic or heteroaryl structure is formed: A stable "C2 heterocyclic" would e.g. be a triazolyl moiety comprising two carbon atoms in the ring and three nitrogen atoms.

In the general formula (Q), L is an electron donating ligand. In one embodiment of the catalysts of general formula (Q) L is a phosphine, sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfonate, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, imidazoline or imidazolidine ligand (the latter two also being jointly referred to as "Im" ligand(s)). With regard to ligand L in general formula (Q):

- the term "phosphinite" includes, for example, phenyl diphenylphosphinite, cyclohexyl dicyclohexylphosphinite, isopropyl diisopropylphosphinite and methyl diphenylphosphinite.

- the term "phosphite" includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert- butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.

- the term "stibine" includes, for example, triphenylstibine, tricyclohexylstibine and trimethylstibine.

- the term "sulfonate" includes, for example, trifluoromethanesulfonate, tosylate and mesylate.

- the term "sulfoxide" includes, for example, (CH₃)₂S(=0) and (C₆H₅)₂S=0.

- the term "thioether" includes, for example, CH₃SCH₃, C₆H₅SCH₃, CH₃OCH₂CH₂SCH₃ and tetrahydrothiophene.

If L is an imidazoline or imidazolidine ligand in the catalysts of general formula (Q), such imidazoline or imidazolidine ligand this may have the same general, preferred, more preferred and most preferred meanings outlined further above with regard to the catalyst of general formula (A)

The ligands X¹ and X² in the catalysts of general formula (Q) may have the same general, preferred, more preferred and most preferred meanings outlined further above with regard to the catalyst of general formula (A)

In the general formula (Q), R¹ shall mean hydrogen, alkyl, alkenyl, alkynyl or aryl. R¹ preferably represents hydrogen, Ci-C₃₀-alkyl, C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl or C₆-C₂₄-aryl. R⁶ is particularly preferably hydrogen. In the general formula (Q) R⁶ shall mean H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, hetero-aryl, - C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂ , - S(=0)₂R, -S(=0)R or a group containing either a C=0 or a C=S structural element adjacent to a carbon atom which is bound to Y in formula (A), wherein R in all occurences is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl. The meanings given for R⁶ as well as R may in each case optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents.

R⁶ in the general formula (Q) is typically Ci-C₃o-alkyl, C₃-C₂o-cycloalkyl, C₂-C₂o-alkenyl, C₂-C₂o- alkynyl, C₆-C₂₄-aryl, C₂-C₂₀ heteroaryl, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, - C(=S)OR, -C(=S)N(R)₂, S(=0)₂N(R)_¾ -S(=0)₂R, -S(=0)R, -CH(R⁶¹)-C(=0)(R⁶²) or -CH(R⁶¹)- C(=S)(R⁶²), wherein R⁶¹ and R⁶² are identical or different and represent alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, or wherein R may represent in the alternative also hydrogen, or where in the alternative R⁶¹ and R⁶² can form a saturated or unsaturated cyclic structure together with the carbon atoms to which they are bound, and wherein in all occurences R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

The preferred meanings given for R⁶, R, R⁶¹ and R⁶² in the general formula (Q) may in each case optionally be substituted by one or more C₁-C30 alkyl, fluoro, chloro, Ci-C₂o alkoxy, C6-C₂₄ aryl or C₂-C₂₀ heteroaryl substituents.

In one preferred embodiment of the catalysts according to general formula (Q) R⁶ is selected from the group consisting of

C3-Cg-cylcoalkyl, straight-chain or branched Ci-Ci₂-alkyl, with the latter being able, if appropriate, to be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or N-R with R as defined above for formula (A), and -CH(R⁶¹)-C(=0)(R⁶²), or -CH(R⁶¹)-C(=S)(R⁶²),wherein R⁶¹ and R⁶² are identical or different and represent alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, wherein R⁶¹ may represent in the alternative also hydrogen or where in the alternative R⁶¹ and R⁶² can form a cyclic structure together with the carbon atoms to which they are bound.

C3-Cs-cycloalkyl encompasses cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. C6-C2 -ar l shall mean an aromatic moiety having from 6 to 24 skeletal carbon atoms. As preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic radicals having from 6 to 10 skeletal carbon atoms, mention may be made by way of example of phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl. Ci-Ci₂-alkyl can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-dodecyl. R⁶ is particularly preferably straight-chain or branched Ci-Ci2-alkyl, most preferably methyl or isopropyl. In the general formula (Q) R², R³, R⁴ and R⁵ are identical or different and can each be hydrogen or an organic or inorganic moiety.

In an appropriate embodiment of the catalysts according to general formula (Q), R², R³, R⁴, R⁵ are identical or different and are each hydrogen, halogen, nitro, cyano, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, -N(R)₂, -Si(R)₃, -0-Si(R)₃, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -C(=S)R, - C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂, -S(=0)R, or -S(=0)₂R wherein R is identical or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound. These meanings given for R², R³, R⁴, R⁵ may be in each case optionally be substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl moieties.

In a preferred embodiment of the catalysts according to general formula (Q) R², R³, R⁴, R⁵ are identical or different and may represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano,

Ci-C₂o-alkyl, C3-Cio-cylcoalkyl, C₂-C₂o-alkenyl, C₂-C₂o-alkynyl, C6-C₂4-aryl, C₂-C₂o heterocyclyl, C₂-C₂o heteroaryl, Ci-C₂o-alkoxy, C₂-C₂o-alkenyloxy, C₂-C₂o-alkynyloxy, C6-C₂4-aryloxy, C₂-C₂o- alkoxycarbonyl, C C_rC₂₀-alkylthio, C₆-C₂₄-arylthio, -N(R)₂, -Si(R)_3, -0-Si(R)_3, -C(=0)R, - C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂, -S(=0)R, or -S(=0)₂R wherein R is identical or different and shall mean H, Ci-C₂o-alkyl, C3-Cio-cycloalkyl,

C₂-Ci6-alkenyl, C₂-C₂o-alkynyl, C6-C₂4-aryl, or C₂-C₂4-heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound. These preferred meanings given for R², R³, R⁴, R⁵ may in each case optionally be substituted by one or more Ci-C3o-alkyl, Ci-C₂o-alkoxy, halogen, C6-C₂4-aryl or heteroaryl moieties.

In a particularly preferred embodiment of the catalysts according to general formula (Q), R², R³, R⁴, R⁵ are identical or different and are each nitro, straight-chain or branched Ci-Cio-alkyl, C₅-Cg- cylcoalkyl, straight-chain or branched CpCio-alkoxy or C6-C₂4-aryl, most preferably phenyl or naphthyl. The CpCio-alkyl and CpCio-alkoxy moieties may optionally be interrupted by one or more double or triple bonds and/or one or more heteroatoms, preferably oxygen or -N(R)- with R being as defined above. Furthermore, two or more of R², R³, R⁴ or R⁵ can also be bridged via aliphatic or aromatic structures. For example, R³ and R⁴ together with the carbon atoms to which they are bound in the phenyl ring of the formula (Q) can form a fused-on phenyl ring so that, overall, a naphthyl structure results.

Suitable catalyst compositions are also obtained using a catalyst of general formula (Ql),

where M, L, X 1¹, X 2 , R 2 , R 3^J,

R 5 ' R 6 , n and E can have the general, preferred and particularly preferred meanings mentioned for the general formula (Q).

The catalysts of the general formula (Ql) are known in principle from e.g., US 2002/0107138 Al (Hoveyda et al.) and can be obtained by preparative methods indicated there.

Particular preference is given to catalyst systems comprising catalysts of the general formula (Ql) in which

M is ruthenium,

X¹ and X² are both halogen, in particular both chlorine,

R⁶ is a straight-chain or branched Ci-C i2-alkyl radical,

R², R³, R⁴, R⁵ have the general, preferred and more preferred meanings mentioned for the general formula (A),

L has the general, preferred and more preferred meanings mentioned for the general formula (A)

E is CH₂ and

n is 0 or 1, more preferably 0.

Special preference is given to catalyst systems comprising catalysts of general formula (Ql) in which

M is ruthenium,

X¹ and X² are both chlorine,

R⁶ is an isopropyl radical,

R², R³, R⁴, R⁵ are all hydrogen, is a substituted or unsubstituted imidazoline or imidazolidine ligand of the formula (Ila) or (lib),

(I la) (l i b)

where

R⁸, R⁹, R¹⁰, R¹¹ are identical or different and represent hydrogen, straight-chain or branched Ci-C3o-alkyl, C3-C2o-cycloalkyl, C2-C2o-alkenyl, C2-C20- alkynyl, C₆-C₂4-aryl, C₇-C2₅-alkaryl, C₂-C₂o heteroaryl, C₂-C₂o heterocyclyl, Ci-C2o-alkoxy, C2-C2o-alkenyloxy, C2-C2o-alkynyloxy, Ce- C2o-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C2o-alkylthio, C6-C2o-arylthio, - Si(R)₃, -0-Si(R)₃, -0-C(=0)R, C(=0)R, -C(=0)N(R)₂, -S0₂N(R)₂ , - S(=0)R, -S(=0)₂R, -0-S(=0)₂R, halogen, nitro or cyano, and

E is CH₂ and

n is 0 or 1 , more preferably 0.

Such meanings of R⁸, R⁹, R¹⁰, and R¹¹ in the specifically preferred catalysts of Formula (Ql) may in each case be substituted by one or more further substituent(s), preferably straight-chain or branched Ci-Cio-alkyl, C3-Cg-cycloalkyl, CpCio-alkoxy or C6-C24-aryl, and these abovementioned substituents may in turn be substituted by one or more moieties, preferably selected from the group consisting of halogen, in particular chlorine or bromine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl.

Very particular preference is given to a catalyst which comes under the general formula (Ql) and has the following struct 2,4,6-trimethylphenyl.

This catalyst is also referred to as "Hoveyda catalyst" in the literature. Further suitable catalysts which come under the general formula (Ql) have the following formulae, where Mes is in each case 2,4,6-trimethylphenyl.

In a further embodiment the process pursuant to the invention can be performed using a catalyst of the general formula (Q2),

where M, L, X¹, X², R¹, R², R⁴, R^~, R⁶, n and E have the general and preferred meanings mentioned for the formula (Q).

The catalysts of the general formula (Q2) are known in principle from, for example WO-A-2004/035596 (Grela) and can be obtained by preparative methods indicated there. Particular preference is given to catalyst of the general formula (Q2) in which

M is ruthenium,

X¹ and X² are both halogen, in particular both chlorine,

R is hydrogen

R⁶ is straight-chain or branched CpCn-alkyl,

R², R⁴, and R⁵ have the general and preferred meanings mentioned for the formula (Q),

L has the meanings mentioned for the general formula (Q),

E is CH₂ and

n is 0 or 1, more preferably 0.

Very particular preference is given to catalyst of the general formula (Q2) in which

M is ruthenium,

X¹ and X² are both chlorine,

R⁶ is isopropyl,

L is a substituted or unsubstituted imidazol or imidazolidine ligand of the formulae

(Ila) or (lib), where R⁸, R⁹, R¹⁰, R¹¹ are identical or different and have the meanings mentioned for the very particularly preferred catalysts of the general formula (Al),

E is CH₂ and

n is 0 or 1, more preferably 0.

Particularly useful catalysts falling under general formula (Q2) have the following structures, where Mes is in each case 2 4,6-trimethylphenyl.

The catalyst depicted on the left is also known as "Grela catalyst" in the literature.

In an alternative embodiment catalysts of the general formula (Q3) can be used in the process of the present invention,

wherein

X¹ and X² are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight- chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C₂o-alkoxy, C6-C24-aryloxy, C3-C₂₀- alkyldiketonate C6-C24-aryldiketonate, Ci-C₂o-carboxylate, Ci-C₂o-alkylsulfonate, C6-C24- arylsulfonate, Ci-C₂o-alkylthiol, C6-C24-arylthiol, Ci-C₂o-alkylsulfonyl or C₁-C₂₀- alkylsulfinyl,

R³ is chloro, fluoro, bromo, -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂ , -C(=S)R, - C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂, -S(=0)₂R, or -S(=0)R,

R⁴ is H, halogen, nitro, cyano, C₁-C₂0 alkyl, C₁-C₂0 alkoxy, C₁-C₂0 alkylthio, -Si(R -0-Si(R)3, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -C(=0)OR, - C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂ , -S(=0)₂R or - S(=0)R,

R² and R⁵ are each H, bromo (Br), iodo (I), C_rC₂o alkyl, C_rC₂o alkoxy, C_rC₂o alkylthio, -Si(R)_3; - 0-Si(R)3, C6-C₂0 aryloxy, C6-C₂0 aryl, C₂-C₂0 heterocyclic, C₂-C₂0 heteroaryl, -C(=0)OR, - C(=0)N(R)₂, , or -S0₂N(R)₂ ,

R⁶ is H, C₁-C₂0 alkyl, C₆-C₂₀ aryl, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -S0₂N(R)₂, or -N(S0₂-R)₂, -S(=0)R, or -S(=0)₂R,

n is 0 or 1

wherein if n=l, then the element

Y^ ( E )_n

(i) if Y and (E)_n are linked by a single bond, then

Y is oxygen (O), sulfur (S), N-R or P-R and

E is CH₂ or

(ii) if Y and (E)_n are linked by a double bond, then

Y is N or P

E is CH, wherein if n=0, then

Y is oxygen (O), sulfur (S), N-R or P-R and directly linked by a single bond to the phenyl moiety depicted above in formula (Q3)

and wherein in all above occurences in formula (Q3)

R is identical or different and shall mean H, Ci-C2o-alkyl, C3-Cio-cycloalkyl, C2-Ci6-alkenyl,

C2-C2o-alkynyl, C6-C24-aryl, or C2-C24-heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound. To the extent the general, preferred, more preferred or most preferred definitions of the catalyst according to general formual (Q3) mentions "C2-C20 heterocyclic" and "C2-C20 heteroaryl" this shall always imply that the respective heterocyclic ring contains besides the number of carbon atoms such a number of hetero atoms that a stable heterocyclic structure is formed: A stable "C2 heteroaryl" would e.g. be an triazolyl moiety comprising two carbon atoms in the ring and three nitrogen atoms.

Definition of X¹ and X² for general formula (Q3)

In the above depicted formula (Q3) the moieties listed as meanings for X¹ and X² can also be substituted by one or more further groups, for example by halogen, preferably fluorine, Ci-Cur alkyl, d-Cio-alkoxy or C6-C24-aryl, where these groups, too, may once again be substituted by one or more substituents selected from the group consisting of halogen, preferably fluorine, C1-C5- alkyl, Ci-C₅-alkoxy and phenyl.

In a preferred embodiment, X¹ and X² are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, Ci-C₅-carboxylate, Ci-C₅-alkyl, phenoxy, C1-C5- alkoxy, Ci-C₅-alkylthiol, C6-C24-arylthiol, C6-C24-aryl or Ci-C₅-alkylsulphonate.

In a particularly preferred embodiment, X¹ and X² are identical and are each halogen, in particular chlorine, CF₃COO, CH₃COO, CFH₂COO, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH₃-C₆H₄-S0₃), mesylate (CH₃S0₃) or trifluoromethanesulphonate (CF₃ S 0₃) .

In a preferred embodiment of the present invention complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions wherein

Y is oxygen or sulfur; X¹ and X² are identical and are each chloro, CF₃COO, CH₃COO, CFH₂COO, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (P-CH₃-C₆H₄-SO₃), mesylate (CH₃SO₃) or trifluoromethanesulphonate (CF₃SO₃),

R³ -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂, chloro, fluoro, bromo,-NR-C(=0)-N(R)₂, or -S0₂N(R)₂,

R⁴ is hydrogen, halogen, nitro, cyano, C₁-C14 alkyl, C₁-C14 alkoxy, C₁-C14 alkylthio, -Si(R)3_; - 0-Si(R)3, C6-C14 aryl, C6-C14 aryloxy, C₂-Ci₄ heterocyclic, C₂-Ci₄ heteroaryl, -C(=0)R, - C(=0)OR, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂, -S0₂N(R)₂, or -N(S0₂-R)₂, -S(=0)R, or - S(=0)₂R

R² and R⁵ are each hydrogen, bromo (Br), iodo (I), C₁-C14 alkyl, C₁-C14 alkoxy, C₁-C14 alkylthio, - Si(R)3_; -0-Si(R)3, C6-C14 aryloxy, C6-C14 aryl, C₂-Ci₄ heterocyclic, C₂-Ci₄ heteroaryl, - C(=0)OR, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂, -S0₂N(R)₂, or -N(S0₂-R)₂,

R⁶ is H, C₁-C14 alkyl, C_rCi₄ alkoxy, C₁-C14 alkylthio, -Si(R)₃, -0-Si(R)₃, C₆-Ci₄ aryl, C₆-Ci₄ aryloxy, C₂-Ci₄ heterocyclic, C₂-Ci₄ heteroaryl, -C(=0)OR, -C(=0)N(R)₂, -NR-C(=0)- N(R)₂, -S0₂N(R)₂, or -N(S0₂-R)₂,

n is 0 or 1

E is CH₂

wherein if n = 1, then Y is linked to E by a single bond,

wherein if n = 0, then Y is directly linked to the phenyl moiety depicted in formula (Q3) and wherein in all above occurences of this preferred embodiment

R is identical or different and shall mean H, CpCg-alkyl, C₅-C6-cycloalkyl, C₂-Cg-alkenyl, C₂-Cg-alkynyl, C6-Ci₄-aryl, or C₂-Ci₄-heteroaryl.

In an even more preferred embodiment complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions wherein

Y is oxygen,

X¹ and X² are identical and each chloro or each R'COO with R' being C₁-C3 alkyl,

R³ -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂, chloro, fluoro, bromo, -NR-C(=0)-N(R)₂,

-S0₂N(R)₂ or -N(S0₂-R)₂,

R² and R⁵ are each hydrogen,

R⁴ is H, chloro, fluoro, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂, -S0₂N(R)₂ or -N(S0₂-R)₂,

R⁶ is C₁-C6 alkyl, particularly isopropyl or isobutyl,

n is 0 or 1

E is CH₂

wherein if n = 1, then Y is linked to E by a single bond,

wherein if n = 0, then Y is directly linked to the phenyl moiety depicted in formula (Q3) and wherein in all above occurences in formula (Q3)

R is identical or different and shall mean H, CpCg-alkyl, C₅-C6-cycloalkyl, C2-Cg-alkenyl, C2-Cg-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl moieties.

In another preferred embodiment of the present invention ruthenium complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions, wherein L can be selected from following structures (Ha), (lib), (lie) and (lid),

(Ma) (l ib) (l ie) (l id) wherein

R¹⁰ and R¹¹ are each C1-C20 alkyl, C6-C20 aryl, C7-C25 alkaryl, C2-C20 heteroaryl, C1-C20 heterocyclic, -C(=0)R, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂, or -S0₂N(R)₂

R⁸ and R⁹ are each hydrogen, C_rC₂o alkyl, C_rC₂o alkoxy, C_rC₂o alkylthio, -Si(R)₃, -0-Si(R)₃,

C6-C20 aryl, C6-C20 aryloxy, C2-C20 heteroaryl, C2-C20 heterocyclic, C(=0)R, - C(=0)N(R)₂, -NR-C(=0)-N(R)₂, or -S0₂N(R)₂ , -S(=0)R, -S(=0)₂R or -0-S(=0)₂R, halogen, nitro or cyano group;

R¹², R¹³ and R¹⁴ are each C1-C20 alkyl, C1-C20 alkoxy, C₆-C₂o aryl, C₆-C₂o aryloxy, C₂-C₂o heteroaryl or C2-C20 heterocyclic group;

wherein in all above occurences regarding structures (Ha), (lib), (lie) and (lid),

R is identical or different and shall mean H, Ci-C2o-alkyl, C3-Cio-cycloalkyl, C2-C16- alkenyl, C2-C2o-alkynyl, C6-C24-aryl, or C6-C24-heteroaryl.

In an even more preferred embodiment complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions, in which the ligand L has the structure (Ila) or (lib) wherein R¹⁰ and R¹¹ are each an aryl group, more preferably each a substituted phenyl group, most preferably each 2,4,6-trimethylphenyl and R⁸ and R⁹ are each hydrogen, respectively.

In another preferred embodiment complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions, in which the ligand L has the structure (lid) wherein R¹², R¹³ and R¹⁴ are each cyclohexyl, respectively.

In another preferred embodiment of the present invention ruthenium complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions, wherein

X¹ and X² are each chloro; L has the general structure (Ila) or (lib) as defined above;

Y is oxygen;

R³ -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂, chloro, fluoro, bromo, -NR-C(=0)-N(R)₂, or -S0₂N(R)₂,

R⁴ is H, halogen, nitro, cyano, C₁-C14 alkyl, C₁-C14 alkoxy, C₁-C14 alkylthio, -Si(R -0-Si(R)3,

C₆-Ci4 aryl, C₆-Ci₄ aryloxy, C₂-Ci₄ heterocyclic, C₂-Ci₄ heteroaryl, -C(=0)R, -C(=0)OR, -

C(=0)N(R)₂, -S(=0)₂R, -S(=0)R or -S0₂N(R)₂,

R² and R⁵ are each H, bromo (Br), iodo (I), C_rCi₄ alkyl, C_rCi₄ alkoxy, C_rCi₄ alkylthio, -0-Si(R)₃,

C6-C14 aryloxy, C6-C14 aryl, C₂-Ci4 heterocyclic, C₂-Ci4 heteroaryl, -C(=0)OR, -

C(=0)N(R)_¾ or -S0₂N(R)₂ ,

R⁶ is H, C1-C14 alkyl C_rCi₄ alkoxy, C_rCi₄ alkylthio, -Si(R)₃, -0-Si(R)₃, C₆-C_l2 aryl, C₆-C_l2 aryloxy, C₂-Ci₂ heterocyclic, C₂-Ci₂ heteroaryl, -C(=0)R, -C(=0)N(R)₂, -NR-C(=0)-N(R)₂,

-S0₂N(R)₂, or -N(S0₂-R)₂,

wherein in all above occurences

R is identical or different and shall mean H, CpCg-alkyl, C₅-C6-cycloalkyl, C₂-Cg-alkenyl, C₂-Cg-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl moieties.

In an even more preferred embodiment of the present invention complex catalysts having the general structure (Q3) are suited for obtaining the novel catalyst compositions, wherein

X¹ and X² are each chloro,

L has the general structure (Ila) or (lib),

Y is oxygen,

R³ chloro, fluoro, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, or -S0₂N(R)₂,

R⁴ is H, chloro, fluoro, -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂, or -S0₂N(R)₂,

R² and R⁵ are each hydrogen,

R⁶ is C₁-C6 alkyl, particularly isopropyl or isobutyl,

wherein in all above occurences

R is identical or different and shall mean H, Ci-C6-alkyl, C₅-C6-cycloalkyl, C₂-C6-alkenyl, C₂-C6-alkynyl, phenyl, imidazolyl, triazolyl, or pyridinyl moieties.

In a particularly preferred embodiment of the present invention a catalyst is used for the process according to the present invention which is selected from the following structures: -44-

-45-

-46-

The above described catalysts of general formula (Q3) with its preferred, more preferred, particularly preferred and most preferred embodiments may be prepared in accordance with the preparation methods described in EP-A-1 905 777.

In one embodiment of the present invention catalysts of general formula (Q4) can be used coming under general formula (I) with n being 1.

wherein M, L, Y, X¹, X², R¹, R², R³, R⁴, R⁵, R⁶ and n have all general, preferred, more preferred and particularly preferred meanings as given for general formula (Q).

General formula (Q4) therefore covers catalysts according to general formula (Q4-1) (with n = 0) and (Q4-2) (with n=l) which can both be used for preparing the catalyst compositions of the present invention

(Q4-1 ) (Q4-2) wherein M, L, Y, X¹, X², R¹, R², R³, R⁴, R⁵, and R⁶ have all general, preferred, more preferred and particularly preferred meanings as given for general formula (Q).

In preferred catalysts to be used for preparing the catalyst compositions according to the invention M is Ruthenium and Y is oxygen or NH with L, X¹, X², R¹, R², R³, R⁴, R⁵, R⁶ and n having all general, preferred, more preferred and particularly preferred meanings as given for general formula

(Q)

Suitable catalysts falling under general formula (Q) and in particular under general formula (Q-2) have the following structures:

ΓΛ

In a specific embodiment of the present invention catalysts of general formula (Q) may be used wherein

R⁶ means either an aryl group, preferably phenyl group substituted in 2-position with C_rCi₀- alkoxy or -N(R)₂, with R being identical or different and representing hydrogen or straight chain or branched Ci-Ce alkyl and

1 2 1 2 3 4 5

wherein M, L, Y, X¹, X^z, R , R^z, R R and R' have the same meanings as given for general formula (Q). In such specific embodiment the substituent R⁶ may then coordinate to the metal of the complex catalyst via the oxygen in the alkoxy group, or the nitrogen in the N(R)₂ substituent. Hence, such specific catalysts then have the general formula (Q)

wherein

Y is oxygen (O) or -NR with R representing hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl,

W is oxygen (O) or NR⁷ with R⁷ being hydrogen or straight chain or branched

Ci-Cio alkyl,

R represents straight chain or branched alkyl,

R¹⁶, R¹⁷, R¹ are identical or different and represent hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, aryl or heteroaryl, and

L, R¹, R², R³, R⁴, R⁵ shall have the general, preferred and more preferred meanings given for general formula (Q)

General formula (Q) covers catalysts according to general formula (Q-l) (with n = 0) and (A5-2) ention,

(Q5-1 ) (Q5-2)

wherein L, Y, X¹, X², R¹, R², R³, R⁴, R⁵, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ have the same meanings as given for general formula (Q5) In preferred catalysts of general formula (Q5) to be used for preparing the catalyst compositions according to the invention

Y is oxygen (O) or -NR with R representing hydrogen, Ci-Cio alkyl, C₅-Cg cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C24 aryl or C2-C20 heteroaryl,

W is oxygen (O) or -NR⁷ with R⁷ being hydrogen or straight chain or branched

C1-C4 alkyl,

R¹⁵ represents straight chain or branched C1-C10 alkyl

R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are identical or different and represent hydrogen, halogen, straight chain or branched C1-C10 alkyl, C₅-Cg cycloalkyl, straight chain or branched C1-C10 alkoxy, C2-C20 alkenyl, C2-C20 alkynyl, C6-C24 aryl or C2-C20 heteroaryl,

L, R¹, R², R³, R⁴, R⁵ shall have the general, preferred and more preferred meanings given for general formula (Q), and

n being 0 or 1.

More preferably catalysts of general formula (Q5) can be used wherein

Y is oxygen (O) or -NR with R representing hydrogen or C1-C4 alkyl,

C1-C4 alkyl,

R¹⁵ represents straight chain or branched C1-C4 alkyl,

R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are identical or different and represent hydrogen, chloro, straight chain or branched C1-C10 alkyl, or straight chain or branched C1-C10 alkoxy and n being 0 or 1.



where

M is ruthenium or osmium, preferably ruthenium, Z is oxygen (O) or sulfur (S),

Y is oxygen (O), sulfur (S), N-R⁷ or P-R⁷, where R⁷ has the meanings indicated below,

X¹ and X² are identical or different ligands,

R¹ is H, alkyl, alkenyl, alkynyl or aryl,

R², R³, R⁴ and R⁵ are identical or different and are each hydrogen, organic or inorganic substituents,

R⁶¹ is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,

R⁶² is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents,

or where in the alternative R⁶¹ and R⁶² may form a cyclic structure together with the two adjacent carbon atoms to which they are bound,

L is a ligand, and

R⁷ is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl which may each be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, and

n is 0 or 1.

The catalysts of the general formula (Q6) are known in principle. Representatives of this class of compounds are the catalysts described by Arlt et al. in WO-A1-2008/034552 and by Zhan in WO- A-2011/079799. The catalysts are commercially available or can be prepared as described in the references cited.

General formula (Q6) covers catalysts according to general formula (Q6-1) (with n = 0) and (Q6-2) (with n=l) which can both be used for preparing the catalyst compositions of the present invention,

(Q6-1 ) (Q6-2)

wherein L, M, X¹, X², R¹, R², R³, R⁴, R⁵, Y, R⁶¹ and R⁶² have the same meanings as given for general formula (Q6). In the catalysts of the general formula (Q6) as well as (Q6-1) and (Q6-2) L is a ligand, usually a ligand having an electron donor function. L can have all meanings as described above relating to general formula (Q). It can in particular represent a P(X³)3 ligand, where X³ are each, independently of one another, Ci-C6-alkyl, C3-Cg-cycloalkyl or aryl or L is a substituted or unsubstituted imidazoline or imidazolidine ligand as defined in general formulae (Ha), (lib), and (Ilia) to (Illn) further above with regard to the catalyst of the general formula (Q).

Alkyl in general formulae (Q6) as well as (Q6-1) and (Q6-2) preferably means Ci-C6-Alkyl which is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1 -ethylpropyl or n-hexyl.

Cycloalkyl in general formulae (Q6) as well as (Q6-1) and (Q6-2) preferably means C3-C8- Cycloalkyl which encompasses cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Aryl in general formulae (Q6) as well as (Q6-1) and (Q6-2) encompasses an aromatic radical having from 6 to 24 skeletal carbon atoms. Preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic radicals having from 6 to 10 skeletal carbon atoms are, for example, phenyl, biphenyl, naphthyl, phenanthrenyl and anthracenyl.

In the catalysts of the general formula (Q6) as well as (Q6-1) and (Q6-2) X¹ and X² are identical or different ligands and can be, for example, hydrogen, halogen, pseudohalogen, straight-chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C2o-alkoxy, C6-C24-aryloxy, C3-C2o-alkyldiketonate, C6-C24- aryldiketonate, Ci-C2o-carboxylate, Ci-C2o-alkylsulphonate, C6-C24-arylsulphonate, C1-C20- alkylthiol, C6-C24-arylthiol, Ci-C2o-alkylsulphonyl or Ci-C2o-alkylsulphinyl.

In the catalysts of the general formula (Q6) as well as (Q6-1) and (Q6-2) the abovementioned ligands X¹ and X² can also be substituted by one or more further substituents, e.g, by halogen, preferably fluorine, Ci-Cio-alkyl, CpCio-alkoxy or C6-C24-aryl, where these substituents may optionally also in turn be substituted by one or more substituents selected from the group consisting of halogen, preferably fluorine, Ci-C₅-alkyl, Ci-C₅-alkoxy and phenyl. In a preferred embodiment of catalyst (Q6) as well as (Q6-1) and (Q6-2) X¹ and X² are identical or different and are each halogen, in particular fluorine, chlorine or bromine, benzoate, C1-C5- carboxylate, Ci-C₅-alkyl, phenoxy, Ci-C₅-alkoxy, Ci-C₅-alkylthiol, C6-C24-arylthiol, C6-C24-aryl or Ci-C₅-alkylsulphonate. In a particularly preferred embodiment of catalyst (Q6) as well as (Q6-1) and (Q6-2) X¹ and X² are identical and are each halogen, in particular chlorine, CF₃COO, CH₃COO, CFH₂COO, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH₃- C₆H₄-S0₃), mesylate (2,4,6-trimethylphenyl) or CF₃S0₃ (trifluoromethanesulphonate). In the catalysts of general formula (Q6) as well as (Q6-1) and (Q6-2) R⁶¹ and R⁶² are identical or different and represent alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, however, R⁶¹ may also represent hydrogen in the alternative.

In the preferred catalyst of general formula (Q6) R⁶¹ and R⁶² are identical or different and preferably represent Ci-C₃o-alkyl, C₃-C2o-cycloalkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, C6-C24-aryl, Ci-C2o-alkoxy, C2-C2o-alkenyloxy, C2-C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, Cp C2o-alkylamino, Ci-C2o-alkylthio, C6-C24-arylthio, Ci-C2o-alkylsulfonyl or Ci-C2o-alkylsulfinyl, each of which may optionally be substituted by one or more alkyl, alkoxy, aryl or heteroaryl substituents, however, R⁶¹ may also represent hydrogen in the alternative, or wherein or where in the alternative R⁶¹ and R⁶² may form a cyclic structure together with the two adjacent carbon atoms to which they are bound, More preferably R⁶¹ is hydrogen and R⁶² is C₃-C2o-cycloalkyl, C6-C24-aryl or straight-chain or branched Ci-Ci2-alkyl, with the latter optionally being able to be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen, or where in the alternative R and R may form a cyclic structure together with the two adjacent carbon atoms to which they are bound. In such preferred definition C3-C2o-cycloalkyl then encompasses, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, C1-C12- alkyl can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1 -ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-dodecyl and C6-C24-aryl radical is an aromatic radical having from 6 to 24 skeletal carbon atoms, more preferably a monocyclic, bicyclic or tricyclic carbocyclic aromatic radical having from 6 to 10 skeletal carbon atoms, most preferably phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

In the general formula (Q6) R¹ is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical. R¹ is preferably hydrogen or a Ci-C3o-alkyl radical, a C2-C2o-alkenyl radical, a C2-C2o-alkynyl radical or a C6-C24-aryl radical. R¹ is particularly preferably hydrogen. In the catalyst of general formula (Q6) R², R³, R⁴ and R⁵ are identical or different and can be H, organic or inorganic substituents. In a preferred embodiment, R², R³, R⁴, R⁵ are identical or different and are each H, halogen, nitro, CF₃, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl, each of which may optionally be substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl substituents. More preferably R², R³, R⁴, R⁵ are identical or different and are H, halogen, preferably chlorine or bromine, nitro, CF₃, Ci-C3o-alkyl, C3-C2o-cycloalkyl, C2-C2o-alkenyl, C₂-C₂o-alkynyl, C₆-C₂4-aryl, d-C₂o-alkoxy, C₂-C₂o-alkenyloxy, C₂-C₂o-alkynyloxy, C₆-C₂4-aryloxy, C2-C2o-alkoxycarbonyl, Ci-C2o-alkylamino, Ci-C2o-alkylthio, C6-C24-arylthio, C1-C20- alkylsulphonyl or Ci-C2o-alkylsulphinyl, each of which may optionally be substituted by one or more Ci-C3o-alkyl, Ci-C2o-alkoxy, halogen, C6-C24-aryl or heteroaryl substituents. In a particularly preferred embodiment, R², R³, R⁴, R⁵ are identical or different and are each nitro, a straight-chain or branched CpCn-alkyl or C6-C2o-cycloalkyl radical, a straight-chain or branched Ci-C2o-alkoxy radical or a C6-C24-aryl radical, most preferably phenyl or naphthyl. The Ci-Ci2-alkyl and C1-C20- alkoxy groups may optionally be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

Furthermore, two or more of R², R³, R⁴ or R⁵ can be bridged via aliphatic or aromatic structures. For example, R³ and R⁴ can, with inclusion of the carbon atoms to which they are bound in the phenyl ring of the formula (Q), form a fused-on phenyl ring so that overall a naphthyl structure results.

Particular preference is given to catalysts of the general formula (Q6) in which M is ruthenium,

Y is oxygen (O),

Z is oxygen (O),

X¹ and X² are both halogen, in particular, both chlorine,

R¹ is hydrogen,

R², R³, R⁴, R⁵ have the general, preferred and more preferred meanings given for the general formula (Q6),

R⁶¹, R⁶¹ have the general, preferred and more preferred meanings given for the general formula (Q6) and

L has the general, preferred and more preferred meanings given for the general formula (Q6).

Very particular preference is given to catalysts of the general formula (Q6) in which

M is ruthenium,

Y is oxygen (O),

Z is oxygen (O),

X¹ and X² are both chlorine,

R¹ is hydrogen,

R², R³, R⁴, R⁵ are all hydrogen,

R⁶¹ is methyl,

R⁶² is methyl and

L is a substituted or unsubstituted imidazoline or imidazolidine ligand of general formulae (Ila), (lib), (Ilia) to (IIIu) as defined for general formula(Q)

A very particularly preferred catalyst which comes under the general structural formula (Q6) has the following structure and is also referred to as "Arlt catal st".

Further suitable catalysts which come under the general formula (Q6) have the formulae depicted below where Mes is in each case a 2,4,6-trimethylphenyl. Even in case this is not shown in the below formulae the double bonded oxygen may also coordinate (back-bite) to the central metal of the complex catalyst

-61-

In a further embodiment catalysts of general formula (Q7) can be used to prepare the novel catalyst compositions

wherein

X¹ and X² are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight- chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C₂o-alkoxy, C6-C24-aryloxy, C3-C₂₀- alkyldiketonate C6-C24-aryldiketonate, Ci-C₂o-carboxylate, Ci-C₂o-alkylsulfonate, C6-C24- arylsulfonate, Ci-C₂o-alkylthiol, C6-C24-arylthiol, Ci-C₂o-alkylsulfonyl or C₁-C₂₀- alkylsulfinyl, L is an electron donating ligand, which can be linked or not linked with X¹ to form a cyclic structure,

Y is NR or PR, preferably NR,

R⁴ is H, halogen, nitro, cyano, Ci-C₂o alkyl, Ci-C₂o alkoxy, Ci-C₂o alkylthio, -Si(R -0-Si(R)3, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -C(=0)OR, - C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂ , -S(=0)₂R or - S(=0)R,

R² and R⁵ are each H, bromo (Br), iodo (I), C_rC₂₀ alkyl, C_rC₂₀ alkoxy, C_rC₂₀ alkylthio, -Si(R)_3; - 0-Si(R)3, C6-C₂o aryloxy, C6-C₂o aryl, C₂-C₂o heterocyclic, C₂-C₂o heteroaryl, -C(=0)OR, - C(=0)N(R)₂, , or -S0₂N(R)₂ ,

R⁶ is H, Ci-C₂₀ alkyl, C₆-C₂₀ aryl, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -S0₂N(R)_¾ -N(S0₂-R)₂, -S(=0)R, or -S(=0)₂R,

and wherein in all above occurences in formula (Q7)

R is identical or different and shall mean H, Ci-C₂o-alkyl, C3-Cio-cycloalkyl, C₂-Ci₆-alkenyl, C₂-C₂o-alkynyl, C6-C₂4-aryl, or C₂-C₂4-heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound.

The following catalysts fall under general formula (Q7) and can be used in the process pursuant to this invention:

/ \

Mes— NL ,N-Mes

Optionally hydrogenated nitrile rubber:

The process according to the invention uses either nitrile rubbers or hydrogenated nitrile rubber as starting rubber for the metathesis reaction.

A Nitrile rubbers

As nitrile rubbers ("NBR"), it is possible to use copolymers or terpolymers which comprise repeating units of at least one conjugated diene, at least one α,β-unsaturated nitrile and optionally one or more further copolymerizable monomers in the metathesis reaction.

The conjugated diene can be of any nature. Preference is given to using (C4-C6) conjugated dienes. Particular preference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof. Very particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Especial preference is given to 1,3-butadiene. As α,β-unsaturated nitrile, it is possible to use any known α,β-unsaturated nitrile, preferably a (C3- C₅) α,β-unsaturated nitrile such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particular preference is given to acrylonitrile. A particularly preferred nitrile rubber is thus a copolymer of acrylonitrile and 1,3 -butadiene.

Apart from the conjugated diene and the α,β-unsaturated nitrile, it is possible to use one or more further copolymerizable monomers known to those skilled in the art, e.g. α,β-unsaturated monocarboxylic or dicarboxylic acids, their esters or amides. As α,β-unsaturated monocarboxylic or dicarboxylic acids, preference is given to fumaric acid, maleic acid, acrylic acid and methacrylic acid. As esters of α,β-unsaturated carboxylic acids, preference is given to using their alkyl esters and alkoxyalkyl esters. Particularly preferred alkyl esters of α,β-unsaturated carboxylic acids are methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2- ethylhexyl methacrylate and octyl acrylate. Particularly preferred alkoxyalkyl esters of α,β- unsaturated carboxylic acids are methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxyethyl (meth)acrylate. It is also possible to use mixtures of alkyl esters, e.g. those mentioned above, with alkoxyalkyl esters, e.g. in the form of those mentioned above.

The proportions of conjugated diene and α,β-unsaturated nitrile in the NBR polymers to be used can vary within wide ranges. The proportion of or of the sum of the conjugated dienes is usually in the range from 40 to 90% by weight, preferably in the range from 60 to 85% by weight, based on the total polymer. The proportion of or of the sum of the α,β-unsaturated nitriles is usually from 10 to 60%) by weight, preferably from 15 to 40% by weight, based on the total polymer. The proportions of the monomers in each case add up to 100% by weight. The additional monomers can be present in amounts of from 0 to 40% by weight, preferably from 0.1 to 40% by weight, particularly preferably from 1 to 30% by weight, based on the total polymer. In this case, corresponding proportions of the conjugated diene or dienes and/or of the α,β-unsaturated nitrile or nitriles are replaced by the proportions of the additional monomers, with the proportions of all monomers in each case adding up to 100% by weight.

The preparation of nitrile rubbers by polymerization of the abovementioned monomers is adequately known to those skilled in the art and is comprehensively described in the polymer literature. In addition nitrile rubbers which can be used for the purposes of the invention are also commercially available, e.g. as products from the product range of the trade names Perbunan® and Krynac® from Lanxess Deutschland GmbH. The nitrile rubbers suited for the metathesis have a Mooney viscosity (ML 1+4 at 100°C) in the range from 30 to 120, preferably from 30 to 70. This corresponds to a number average molecular weight M_n in the range 200,000 - 700,000, preferably in the range 200,000 - 400,000. The nitrile rubbers used also have a polydispersity PDI = M_w/M_n, where M_w is the weight average molecular weight and M_n is the number average molecular weight, in the range 2.0 - 6.0 and preferably in the range 2.0 - 4.0. The determination of the Mooney viscosity is carried out in accordance with ASTM standard D 1646. The determination of the number average molecular weight is carried out by GPC in accordance with DIN 55672-1. The nitrile rubbers obtained by the metathesis process according to the present invention have a

Mooney viscosity (ML 1+4 at 100°C) in the range of from 3 to 30, preferably of from 10 to 20. This corresponds to a weight average molecular weight M_win the range of from 2,000 to 500,000, preferably in the range of from 25,000 to 200,000. The nitrile rubbers obtained have a polydispersity PDI = M_w/M_n, where M_n is the number average molecular weight, in the range of from 1.5 to 6.0, preferably in the range of from 1,7 - 3,5.

B Hydrogenated nitrile rubbers

Instead of using nitrile rubbers it is also possible to subject hydrogenated nitrile rubbers to the process pursuant to the invention.

However, at least 1 % of the originally contained C=C double bonds of the nitrile rubber should still be present in order to allow a metathetic degradation. In such HNBR which may be used the C=C double bonds present in the starting nitrile rubber prior to hydrogenation are saturated to an extent of at least 50%, preferably 70-99%, particularly preferably 80-98%).

The HNBR to be subjected to the process pursuant to the invention typically has a Mooney viscosity (ML 1+4 at 100°C), measured in accordance with ASTM standard D 1646, in the range 3-65, preferably from 10 to 40. This corresponds to a weight average molecular weight M_win the range 2000-400 000 g/mol, preferably in the range 20 000-200 000. The hydrogenated nitrile rubbers furtheron have a polydispersity PDI = M_w/M_n, where M_w is the weight average molecular weight and M_n is the number average molecular weight, in the range 1-5 and preferably in the range 1.5-3.

Such HNBR may be obtained by a hydrogenation of nitrile rubbers which may be carried out in the manner sufficiently known to those skilled in the art (see e.g. US-A-6,683,136) using either homogeneous or heterogeneous hydrogenation catalysts. Suitable catalysts and solvents for a hydrogenation in the homogeneous phase are described e.g. in DE-A-25 39 132 and EP-A-0 471 250. When heterogeneous catalysts are used, these are usually supported catalysts based on palladium which are, for example, supported on carbon, silica, calcium carbonate or barium sulphate. It is usually carried out by treating the nitrile rubber to be hydrogenated in a solvent such as toluene or monochlorobenzene with hydrogen at a temperature in the range from 100 to 150°C and a pressure in the range from 50 to 150 bar for from 2 to 10 hours.

It is also possible to carry out the subsequent metathetic degradation of the hydrogenated nitrile rubbers in situ, i.e. in the same reaction vessel in which the hydrogenation has previously also been carried out and without the necessity of isolating the hydrogenated nitrile rubber. The metathesis catalyst as well as the ionic liquid is simply added to the reaction vessel.

Co-olefin:

The metathesis reaction according to the present invention may be carried out in absence or the presence of a co-olefin, which is preferably a C2 to Ci6 linear or branched olefin such as ethylene, isobutene, styrene or 1-hexene. Where the co-olefin is a liquid (such as 1-hexene), the amount of co-olefin employed is preferably in the range of from 1 to 200 weight %. Where the co-olefin is a gas (such as ethylene) the amount of co-olefin employed is such that it results in a pressure in the reaction vessel in the range of from 1 * 10⁵ Pa to 1 * 10⁷ Pa, preferably in the range of from 5.2 * 10⁵ Pa to 4 * 10⁶ Pa.. Preferably the metathesis reaction is performed using 1-hexene.

Solvent:

Besides the essential presence of the ionic liquid the process of the present invention can be carried out in the presence of an additional solvent which does not inactivate the catalyst or otherwise interfere with the reaction and which, for example, makes it easier to separate the products from the ionic liquid and the catalyst present therein. In the presence of a solvent and the ionic liquids, a heterogeneous catalyst system is obtained when ionic catalysts or catalysts which dissolve preferentially in the ionic liquid are used. After the metathesis reaction is complete, the ionic phase comprising the catalyst can easily be separated from the additive and the reaction product present therein. The catalyst in the ionic liquid can be used for further metathesis reactions without intermediate purification steps.

Suitable organic solvents are, in particular, halogenated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, 1 ,2-dichloroethane or trichloroethane, aromatic compounds such as benzene, toluene, xylene, cumene or halogenobenzenes, preferably monochlorobenzene (MCB), alkanes, preferably C₅-C2o-alkanes, such as pentane, hexane or cyclohexane, esters such as tert-butylmethyl esters or acetic esters, ethers such as diethyl ether, tetrahydrofuran and di- methoxyethane, amides such as dimethylformamide, acetone, dimethyl carbonate or alcohols. In certain cases if a co-olefin is used which can itself act as a solvent (for example, 1-hexene) no other solvent is necessary.

The advantage of ionic liquids is that they are immiscible with lots of other solvents, in particular aliphatic and aromatic hydrocarbons. In organic reactions for which the use of a catalyst is necessary, heterogeneous catalysis can be achieved by addition of ionic liquids and a suitable catalyst which dissolves only or preferentially in the ionic liquid.

The concentration of the optionally hydrogenated nitrile rubber in the reaction mixture is not critical but, obviously, should be such that the reaction is not hampered if the mixture is too viscous to be stirred efficiently, for example. Preferably, the concentration of (H)NBR is in the range of from 1 to 20% by weight, most preferably in the range of from 6 to 15% by weight of the total mixture mainly consisting of the (H)NBR, the catalyst, ionic liquid, optionally the co-olefin and optionally the additional solvent.

The metathesis reaction is carried out at a temperature in the range of from 15 to 140°C; preferably in the range of from 20 to 80°C.

The amount of metathesis catalyst based on the optionally hydrogenated nitrile rubber used depends on the nature and the catalytic activity of the specific catalyst. The amount of catalyst used is usually from 1 to 1000 ppm of noble metal, preferably from 2 to 500 ppm, in particular from 5 to 250 ppm, based on the nitrile rubber used.

The reaction time depends on a number of factors, for example, on the type of NBR, the type of catalyst, the catalyst concentration used and the reaction temperature. The reaction is typically complete within three hours under normal conditions. The progress of the metathesis can be monitored by standard analytical methods, e.g. by GPC measurement or by determination of the viscosity. EXAMPLES:

The metathesis reactions were carried out in 1L glass containers under the following conditions:

Cement Concentration* 15% by weight

Co-Olefin 1 -Hexene

Co-Olefin Concentration 4 hr

Catalyst l,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)

(tricyclohexylphosphine)-Ruthenium(phenyl methylene) dichloride (Grubb's 2^nd Generation catalyst (NGG)) (Materia Inc., U.S.A.)

Catalyst Loading See Tables 1 and 2

Solvent Monochlorobenzene

Ionic Liquid See the respective Example

Perbunan^® T 3429 (Nitrile Rubber) statistical butadiene-acrylonitrile copolymer with an acrylonitrile content of 34 mol% and a Mooney- Viscosity (ML (l+4)@ 100 °C) of 29 MU. (Lanxess Deutschland GmbH, Germany)

* "Cement Concentration" means the concentration of the nitrile rubber in the reaction mixture.

EXAMPLE 1 :

Ionic liquid: l-ethyl-3-methyl-pyridinium ethylsulfate

15 g of Perbunan ^® T 3429 was dissolved in 100 g monochlorobenzene in a container. 0,015 g of l,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(tricyclohexylphosphine)-Ruthenium

(phenyl-methylene) dichloride in 50 g of an l-ethyl-3-methyl-pyridinium ethylsulfate as ionic liquid was added to the container. The reaction mixture was allowed to react for a period of 60 min at a temperature of 22°C while being agitated. After the set time allotment was complete, the reaction was allowed to phase separate and the ionic liquid layer was separated from the organic solvent/rubber layer through the use of a separation funnel. The organic layer was reacted with water in order to coagulate the mixture and isolate the rubber product.

The progress of the reaction was monitored using GPC in accordance with DIN 55672-1. Table 1

* Perbunan^® T 3429

EXAMPLE 2:

Example 2 was carried out in the same manner as Example 1 with the exception that for the metathesis reaction 0,005phr of Grubbs II catalyst was used.

The progress of the reaction was monitored by GPC in accordance with DIN 55672-1 (see Table 2).

Table 2

* Perbunan^® T 3429 COMPARATIVE EXAMPLES:

The Comparative Examples were carried out in the exact same manner as Example 1 with the exception that no ionic liquid was used for the metathesis reaction and an amount of the Grubbs II catalyst identified in Table 3.

Table 3

Metathesis Mn Mw PDI

Catalyst (phr) (g/mol) (g/mol)

None 69,093 217,443 3, 15

0,004 70,000 198,000 2,85

0,006 69,000 185,000 2,69

0,008 62,000 169,000 2,71 Comparing the results from Tables 1 and 2 with the results from Table 3 one can observe that the presence of the ionic liquid enhances the metathesis reaction. With performing a metathesis reaction of Perbunan^® T 3429 in the absence of an ionic liquid and utilizing 0,008 phr of Grubbs II catalyst, one does not reach the low level of molecular weight as well as polydispersity reached in the same reaction if performed in the presence of ionic liquids with 0,005 phr of Grubbs II catalyst.

Claims

WHAT IS CLAIMED IS:

1. A process for reducing the molecular weight of an optionally hydrogenated nitrile rubber by subjecting the optionally hydrogenated nitrile rubber to a metathesis reaction in the presence of at least one ionic liquid and a transition metal complex catalyst having at least one ligand bound in a carbene-like fashion to the center metal of the complex catalyst.

2. The process according to claim 1, wherein the ionic liquid is a salt or salt mixture which is liquid in a temperature range of from -20°C to 300°C, preferably of from 0°C to 150°C, and particularly preferably of from 20°C to 100°C.

3. The process according to claim 1, wherein the process is performed in the presence of at least one ionic liquid which is selected from the group consisting of the ionic liquids

(5)

wherein

A^n" shall mean an anion selected from the group consisting of hexafluorophosphate (PF₆ ^~), nitrate (NO₃)^", halides, preferably fluoride, chloride, bromide or iodide, sulfates, sulfonates, aluminates, carboxylates, phosphates and borates, with n meaning 1, 2 or 3 depending on the negative charge of the aforementioned anions and (1/n) therefore representing 1 for a one time negatively charged anion, 1/2 for a two times negatively charged anion and 1/3 for a three times negatively charged anion,

X is nitrogen or phosphorous,

The process according to claim 3, wherein the ionic liquid is selected from the group consisting of the ionic liquids having the general formulae (l)-(5) wherein n is 1 and A- represents PF₆ ^", N0₃ ^", F^", CI^", Br , Γ, R⁷S0₃ ^", R⁷OS0₃ ^", R⁷C0₃ ^~, BF₄ ^", and

B(R⁷)₄ ^~, where R⁷ is identical or different and represents alkyl, substituted alkyl, aryl, more preferably phenyl, substituted aryl, or alkoxy.

The process according to claim 1 wherein the ionic liquid is selected from the group consisting of l-ethyl-3-methyl-pyridinium ethylsulfate, l-ethyl-3-methyl-imidazolium ethylsulfate, l-methyl-3-butylimidazolium chloride, l-methyl-3-ethylimidazolium chloride, N-butylpyridinium chloride, tetrabutylphosphonium chloride, ammonium hexa- fluorophosphate, ammonium tetrafluoroborate, ammonium tosylate, ammonium hydrogen sulphate, pyridinium hexafluorophosphate, l-methyl-3 -butyl imidazolium hexafluoro- phosphate, pyridinium tetrafluoroborate, pyridinium hydrogen sulphate, N-butylpyridinium hexafluorophosphate and combinations of two or more of the aforementioned ionic liquids.

The process according to claim 1, wherein the optionally hydrogenated nitrile rubber contains repeating units derived from at least one α,β-unsaturated nitrile and at least one conjugated diene.

The process according to claim 6, wherein the optionally hydrogenated nitrile rubber contains repeating units derived from at least one conjugated diene selected from the group consisting of 1 ,2-butadiene, 1,3 -butadiene, isoprene, 2,3-dimethylbutadiene, piperylene and mixtures thereof, preferably 1,3-butadiene, and of at least one α,β-unsaturated nitrile selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and mixtures thereof, preferably acrylonitrile.

8. The process according to claim 6 or 7, wherein the optionally hydrogenated nitrile rubber additionally contains repeating units derived from at least one further copolymerizable termonomer, preferably selected from the group consisting of α,β-unsaturated monocarboxylic acids, their esters, their amides, α, β -unsaturated dicarboxyhc acids, their monoesters or diesters, or their corresponding anhydrides or amides.

The process according to claim 1, wherein the complex catalyst used is selected from the group consisting of

(i) catalysts of general formula (A),

where

M is osmium or ruthenium,

X¹ and X² are identical or different and are two ligands, preferably anionic ligands, L are identical or different ligands, preferably uncharged electron donors,

R are identical or different and are each hydrogen, alkyl, preferably Ci-C3o.alkyl, cycloalkyl, preferably C3-C₂o-cycloalkyl, alkenyl, preferably C₂-C₂o-alkenyl, alkynyl, preferably C₂-C₂o-alkynyl, aryl, preferably C6-C24-aryl, carboxylate, preferably Ci-C₂o-carboxylate, alkoxy, preferably Ci-C₂o-alkoxy, alkenyloxy, preferably C₂-C₂o-alkenyloxy, alkynyloxy, preferably C₂-C₂o-alkynyloxy, aryloxy, preferably C6-C24-aryloxy, alkoxycarbonyl, preferably C₂-C₂₀- alkoxycarbonyl, alkylamino, preferably Ci-C3o-alkylamino, alkylthio, preferably Ci-C3o-alkylthio, arylthio, preferably C6-C24-arylthio, alkylsulphonyl, preferably Ci-C₂o-alkylsulphonyl, or alkylsulphinyl, preferably Ci-C₂o-alkylsulphinyl, where these groups may in each case optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moities or, as an alternative, the two groups R together with the common carbon atom to which they are bound are bridged to form a cyclic structure which can be aliphatic or aromatic in nature, may be substituted and may contain one or more heteroatoms,

(ii) catalysts

where

n is 0, 1 or 2,

m is 0, 1 , 2, 3 or 4 and

R^' are identical or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals which may in each case be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl,

catalysts of general formula (B),

where

M is ruthenium or osmium,

X¹ and X² are identical or different and are anionic ligands,

R^" are identical or different and are organic moieties,

Im is a substituted or unsubstituted imidazoline or imidazolidine ligand and

An is an anion,

(iv) catalysts of general formula (C)

where

M is ruthenium or osmium,

R¹³ and R¹⁴ are each, independently of one another, hydrogen, Ci-C2o-alkyl, C2-C20- alkenyl, C2-C2o-alkynyl, C6-C24-aryl, Ci-C2o-carboxylate, Ci-C2o-alkoxy, C2-C20- alkenyloxy, C2-C2o-alkynyloxy, C6-C24-aryloxy, C2-C2o-alkoxycarbonyl, C1-C20- alkylthio, Ci-C2o-alkylsulphonyl or Ci-C2o-alkylsulphinyl,

X³ is an anionic ligand,

L² is an uncharged π-bonded ligand which may either be monocyclic or polycyclic, L³ is a ligand selected from the group consisting of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines,

Y^" is a noncoordinating anion and

n is 0, 1, 2, 3, 4 or 5,

catalysts of general formula (D),

where

M is ruthenium or osmium,

X¹ and X² are identical or different and are anionic ligands which can have all meanings of X¹ and X² mentioned in the general formulae (A) and (B),

L represent identical or different ligands which can have all general and preferred meanings of L mentioned in the general formulae (A) and (B),

R¹⁹ and R²⁰ are identical or different and are each hydrogen or substituted or unsubstituted alkyl,

(E) (F)

(G)

where

M is osmium or ruthenium,

X¹ and X² are identical or different and are two ligands, preferably anionic ligands, L is a ligand, preferably an uncharged electron donor, Z¹ and Z² are identical or different and are uncharged electron donors,

R²¹ and R²² are each, independently of one another, hydrogen alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulphonyl or alkylsulphinyl which are in each case substituted by one or more substituents selected from among alkyl, halogen, alkoxy, aryl or heteroaryl,

(vii) catalysts (N) comprising the general structural element (Nl), where the carbon atom denoted by "*" is bound via one or more double bonds to the catalyst framework having a

and where

R²⁵-R³² are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF₃, nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (-S0₃ ^~), -OS0₃ ^~, -P0₃ ^" or OP0₃ ^" or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where all these moieties can each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl substituents, or, as an alternative, two directly adjacent substituents from the group consisting of R²⁵-R³² together with the ring carbons to which they are bound form a cyclic group, preferably an aromatic system, by bridging or, as an alternative, R⁸ is optionally bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst,

m is 0 or 1 and

A is oxygen, sulphur, C(R³³R³⁴), N-R³⁵, -C(R³⁶)=C(R³⁷)-, -C(R³⁶)(R³⁸)-C(R³⁷)(R³⁹)-, where R³³-R³⁹ are identical or different and can each have the same meanings as (viii) c

(N2a) (N2b)

where

M is ruthenium or osmium,

X¹ and X² are identical or different and are two ligands, preferably anionic ligands, L¹ and L² are identical or different ligands, preferably uncharged electron donors, where L² can alternatively also be bridged to the radical R⁸,

n is 0, 1 , 2 or 3, preferably 0, 1 or 2,

n^' is 1 or 2, preferably 1 , and

R²⁵-R³², m and A have the same meanings as given in general formula (Nl), and

(ix) catalysts of general formula (Q)

where

M is ruthenium or osmium,

X¹ and X² are identical or different ligands,

R¹ is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl and R², R³, R⁴ and R⁵ are identical or different and are each hydrogen or an organic or inorganic substituent, R⁶ is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, -C(=0)R, - C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, - S(=0)₂N(R)₂, -S(=0)₂R, -S(=0)R or a group containing either a C=0 or a C=S structural element adjacent to a carbon atom which is bound to Y, n is 0 or 1 ,

wherein if n=l, then the element

Y^(E)_n

(i) if Y and (E)_n are linked by a single bond, then

Y is oxygen (O), sulfur (S), N-R or P-R, and

E is CH₂ or

(ii) if Y and (E)_n are linked by a double bond, then

Y is N or P, and

E is CH

wherein if n=0, then

and wherein in all above occurences of general formula (Q)

R is hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

The catalyst composition according to claim 1, wherein a catalyst is used which is selected from the group consisting of

(i) catalysts of general formula (Ql),

wherein M, L, X 1¹, X 2 , R 2 , R 3^J, R 4^, R 5 ' R 6 , n and E can have the meanings mentioned for the general formula (Q) in claim 9,

(ii) catalysts of general formula (Q2),

wherein M, L, X 1, X 2, R 1, R2, R 4, R 5, R 6, n and E have the general and preferred meanings mentioned for the formula (Q) in claim 9,

(iii) catalysts of general formula (Q3)

where

X¹ and X² are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight-chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C₂o-alkoxy, C6-C24- aryloxy, C3-C₂o-alkyldiketonate C6-C24-aryldiketonate, Ci-C₂o-carboxylate, Cp C₂o-alkylsulfonate, C6-C24-arylsulfonate, Ci-C₂o-alkylthiol, C6-C24-arylthiol, Cp C₂o-alkylsulfonyl or Ci-C₂o-alkylsulfinyl,

R³ is chloro, fluoro, bromo, -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂ , -

C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂, -S(=0)₂R, or - S(=0)R,

R⁴ is H, halogen, nitro, cyano, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, -Si(R)3_;

-0-Si(R)3, C6-C20 aryl, C6-C20 aryloxy, C2-C20 heterocyclic, C2-C20 heteroaryl, -

C(=0)R, -C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -

C(=S)N(R)₂, -S(=0)₂N(R)₂ , -S(=0)₂R or -S(=0)R,

R² and R⁵ are each H, bromo (Br), iodo (I), C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio,

-Si(R)₃, -0-Si(R)₃, C₆-C₂o aryloxy, C₆-C₂o aryl, C₂-C₂o heterocyclic, C₂-C₂o heteroaryl, -C(=0)OR, -C(=0)N(R)₂, , or -S0₂N(R)₂ , R⁶ is H, C1-C20 alkyl, C₆-C₂₀ aryl, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -

C(=0)OR, -C(=0)N(R)₂, -S0₂N(R)_¾ or-N(S0₂-R)₂, -S(=0)R, or -S(=0)₂R, n is 0 or 1

wherein if n=l, then the element

Y^(E)_n

shall mean that Y and (E)_nare linked either by a single bond or by a double bond, wherein

(i) if Y and (E)_n are linked by a single bond, then

Y is oxygen (O), sulfur (S), N-R or P-R and

E is CH₂ or

(ii) if Y and (E)_n are linked by a double bond, then

Y is N or P

E is CH,

wherein if n=0, then

and wherein in all above occurences in formula (Q3)

R is identical or different and shall mean H, Ci-C₂o-alkyl, C3-Cio-cycloalkyl, C₂-Ci6- alkenyl, C₂-C₂o-alkynyl, C6-C₂4-aryl, or C₂-C₂4-heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound,

(iv) c

wherein M, L, Y, X¹, X², R¹, R², R³, R⁴, R⁵, R⁶ and n have the meanings given for general formula (Q) in claim 9,

(v) catalysts of general formula (Q5)

where

W is oxygen (O) or NR⁷ with R⁷ being hydrogen or straight chain or branched

Ci-Cio alkyl,

R¹⁵ represents straight chain or branched alkyl,

R¹⁶, R¹⁷, R¹⁸ and R¹⁹ are identical or different and represent hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, aryl or heteroaryl, and L, R¹, R², R³, R⁴, R⁵ and n shall have the meanings given for general formula (Q) in claim

9, catalysts o

where

M is ruthenium or osmium, preferably ruthenium,

Z is oxygen (O) or sulfur (S),

Y is oxygen (O), sulfur (S), N-R⁷ or P-R⁷, where R⁷ has the meanings indicated below, X¹ and X² are identical or different ligands,

R¹ is H, alkyl, alkenyl, alkynyl or aryl, R², R³, R⁴ and R⁵ are identical or different and are each hydrogen, organic or inorganic substituents,

L is a ligand,

n is 0 or 1 , and

(vii) catalysts of general formula (Q7)

where

X¹ and X² are identical or different and shall mean hydrogen, halogen, pseudohalogen, straight-chain or branched Ci-C3o-alkyl, C6-C24-aryl, Ci-C2o-alkoxy, C6-C24-aryloxy, C3-C2o-alkyldiketonate C6-C24-aryldiketonate, Ci-C2o-carboxylate, C1-C20- alkylsulfonate, C6-C24-arylsulfonate, Ci-C2o-alkylthiol, C6-C24-arylthiol, C1-C20- alkylsulfonyl or Ci-C2o-alkylsulfinyl,

Y is NR or PR, preferably NR, R³ is chloro, fluoro, bromo, -C(=0)R, -C(=0)OR, -OC(=0)R, -C(=0)N(R)₂ , -C(=S)R, -

C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -S(=0)₂N(R)₂, -S(=0)₂R, or -S(=0)R, R⁴ is H, halogen, nitro, cyano, Ci-C₂o alkyl, Ci-C₂o alkoxy, Ci-C₂o alkylthio, -Si(R)3_; -0-

Si(R)₃, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R,

-C(=0)OR, -C(=0)N(R)₂, -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R)₂, -

S(=0)₂N(R)₂ , -S(=0)₂R or -S(=0)R,

R² and R⁵ are each H, bromo (Br), iodo (I), Ci-C₂₀ alkyl, Ci-C₂₀ alkoxy, Ci-C₂₀ alkylthio,

-Si(R)3_; -0-Si(R)3, C6-C₂o aryloxy, C6-C₂o aryl, C₂-C₂o heterocyclic, C₂-C₂o heteroaryl,

-C(=0)OR, -C(=0)N(R)₂, , or -S0₂N(R)₂ ,

R⁶ is H, Ci-C₂₀ alkyl, C₆-C₂₀ aryl, C₂-C₂₀ heterocyclic, C₂-C₂₀ heteroaryl, -C(=0)R, -

C(=0)OR, -C(=0)N(R)₂, -S0₂N(R)_¾ -N(S0₂-R)₂, -S(=0)R, or -S(=0)₂R, and wherein in all above occurences in formula (Q7)

R is identical or different and shall mean H, Ci-C₂o-alkyl, C3-Cio-cycloalkyl, C₂-Ci₆- alkenyl, C₂-C₂o-alkynyl, C6-C₂4-aryl, or C₂-C₂4-heteroaryl, or if two substituents R are bound to the same atom, such two substituents R may also form a saturated or unsaturated cyclic structure together with the atoms to which they are bound.

1 1. The process according to claim 1 , wherein the amount of the catalyst is from 1 to 1000 ppm of noble metal, preferably from 2 to 500 ppm, in particular from 5 to 250 ppm, based on the optionally hydrogenated nitrile rubber used.

12. The process of claim 1 , further comprising the presence of a co-olefin.

13. The process according to claim 12, wherein the co-olefin is selected from the group consisting of C₂ to Ci6 linear or branched olefins, more preferably selected from the group consisting of ethylene, isobutene, styrene and hexene.

14. The process according to claim 1 , further comprising at least one organic solvent. 15. The process according to claim 14, wherein monochlorobenzene is used as organic solvent.

16. The process according to one claim 15, wherein the transition metal complex catalyst is recovered from the ionic liquid after the completion of the metathesis reaction and recyled.