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GROUP 8 TRANSITION METAL CATALYSTS AND METHOD FOR MAKING SAME AND PROCESS FOR USE OF SAME IN METATHESIS REACTION

20170145152 ยท 2017-05-25

    Inventors

    Cpc classification

    International classification

    Abstract

    Metal catalyst compounds are disclosed. The catalyst compound are represented by the formula (I-II and VII): wherein M is a Group 8 metal; X is an anionic ligand; L is a neutral two electron donor ligand; K 2 (A-E) is a ditopic or multitopic ligand. Also disclosed is an easy applicable catalyst synthesis and the application in different olefin metathesis processes, e.g. Reaction Injection Molding (RIM), rotational molding, vacuum infusion, vacuum forming, process for conversion of fatty acids and fatty acid esters or mixtures thereof, in -olefins, dicarboxylic acids or dicarboxylic esters, etc.

    Claims

    1. Group 8 transition metal catalysts having general structures of formulas (I) or (II): ##STR00072## wherein M is a Group 8 transition metal; R.sup.1-R.sup.6 are identical or different and selected from hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups except that R.sup.2 does not represent phenyl when R.sup.1R.sup.3R.sup.4R.sup.5R.sup.6H; wherein alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures; X.sup.1 preferably represents an anionic ligand; L.sup.1 preferably represent a neutral electron donor; A.sup.1 and A.sup.2 are identical or different and are selected from the group consisting of oxygen, sulphur, selenium, NR, PR, POR, AsR, AsOR, SbOR and SbR; T.sup.1 and T.sup.2 are identical or different and selected from the group consisting of ##STR00073## wherein E represent preferably a donor atom selected from the group consisting of nitrogen, phosphor, oxygen, sulphur, and selenium; wherein for the group ##STR00074## in case of oxygen, sulphur and selenium, R is omitted for double bonded E or R remains for a single bonded E; wherein for the group ##STR00075## in case of oxygen, sulphur and selenium, the E-C bound is a single bond and the C atom contains an extra R group or the CR is a double bond or the CR is a double bond; C.sup.1 and C.sup.2 are carbon atoms linked to each other via a single or double bond wherein in case of a single bond each carbon atom bears an extra substituent R.sup.C1 and R.sup.C2; R, R, R, R and R are identical or different and selected from H, hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; wherein alternatively in each case two directly adjacent radicals from the group of R, R, R, R and R, including the atoms to which they are attached, generating one or more cyclic structures, including aromatic structures; R.sup.C1 and R.sup.C2 are identical or different and are as defined for R, R, R and R.

    2. The catalysts according to claim 1, wherein M is Ru or Os.

    3. The catalysts according to claim 1, wherein L.sup.1 is selected from phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, phosphite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, pyrazine, thiocarbonyl, thioether, triazole carbene, N-Heterocyclic carbene, substituted NHC, and a cyclic alkyl amino carbene.

    4. The catalysts according to claim 1, wherein ligand L.sup.1 represent a phosphine ligand having the formula P(Q.sup.1).sub.3 with Q.sup.1 are identical or different and are alkyl, preferably C.sub.1-C.sub.10 alkyl, more preferably C.sub.1-C.sub.5-alkyl, cycloalkyl-, preferably C.sub.3-C.sub.20 cycloalkyl, more preferably C.sub.3-C.sub.8 cycloalkyl, preferably cyclopentyl, cyclohexyl, and neopentyl, aryl, preferably C.sub.6-C.sub.24 aryl, more preferably phenyl or toluyl, alkyl-phosphabicyclononane, C.sub.3-C.sub.20 cycloalkyl phospha-bicyclononane, a sulfonated phosphine ligand of formula P(Q.sup.2).sub.3 wherein Q.sup.2 represents a mono- or poly-sulfonated Q.sup.1-ligand; C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10-alkyl-phosphinite ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl phosphonite ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl phosphite-ligand, a C.sub.6-C.sub.24aryl C.sub.1-C.sub.10 alkyl arsine ligand, a C.sub.6-C.sub.24aryl or C.sub.1-C.sub.10 alkyl amine ligands, a pyridine ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl-sulfoxide ligand, a C.sub.6-C.sub.24-aryl or C.sub.1-C.sub.10 alkyl ether ligand or a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl amide ligands which all can be multiply substituted, for example by a phenyl group, wherein these substituents are in turn optionally substituted by one or more halogen, C.sub.1-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy radicals.

    5. The catalysts according to claim 1, wherein ligands L.sup.1 represent a pyridine ligand which in this application is a generic term and include all the unsubstituted and substituted nitrogen-containing ligands described in WO-A-03/011455 and U.S. Pat. No. 6,759,537 B2; examples are: pyridine, picolines (-, -, and -picoline), lutidines (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 (2-, 3- and 4-chloropyridine), bromopyridines (2-, 3- and 4-bromopyridine), nitropyridines (2-, 3- and 4-nitropyridine), bipyridine, picolylimine, gamma-pyran, phenanthroline, pyrimidine, bipyrimide, pyrazine, indole, coumarine, carbazole, pyrazole, pyrrole, imidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine benzimidazole, bisimidazole, bisoxazole pyrrole, imidazole and phenylimidazole.

    6. The catalysts according to claim 1, wherein ligand L.sup.1 represent a N-Heterocyclic carbene (NHC) having a general structure of the formulas (IIIa) or (IIIb), ##STR00076## wherein R.sup.7-R.sup.14, R.sup.11, R.sup.12 are identical or different and are hydrogen, straight or branched C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20, alkynyloxy, C.sub.6-C.sub.20 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio, C.sub.6-C.sub.20 arylthio, C.sub.1-C.sub.20 alkylsulfonyl, C.sub.1-C.sub.20 alkyl sulfonate, C.sub.6-C.sub.20 aryl sulfonate or C.sub.1-C.sub.20 alkyl sulfinyl, and one or more of the radicals R.sup.7-R.sup.14, R.sup.11, R.sup.12 can independently of one another be substituted by one or more substituents, preferably straight or branched C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.10 alkoxy or C.sub.6-C.sub.24 aryl, where these aforementioned substituents may in turn be substituted by one or more radicals, preferably selected from the group comprising halogen, especially chlorine or bromine, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy and phenyl.

    7. The catalysts according to claim 1, wherein ligands L.sup.1 represent a cyclic alkyl amino carbenes (CAACs) having a general structure of the Formula (VI): ##STR00077## wherein the ring A is a 4-, 5-, 6-, or 7-membered ring, and Z is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S and Si with available valences optionally occupied by hydrogen, oxo or R-substituents, wherein R is independently selected from the group comprising C.sub.1 to C.sub.12 hydrocarbyl groups, substituted C.sub.1 to C.sub.12 hydrocarbyl groups, and halides, and each R.sup.15 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluyl, chlorophenyl, phenol, or substituted phenol.

    8. The catalysts according to claim 1, wherein X.sup.1 is selected from hydrogen, halogen, nitrate, pseudohalogen, straight-chain or branched C.sub.1-C.sub.30-alkyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 alkylthiol, C.sub.6-C.sub.24 arylthiol, C.sub.1-C.sub.20 alkoxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.24 alkoxycarbonyl, C.sub.6-C.sub.20 aryloxycarbonyl, C.sub.2-C.sub.20 acyl, C.sub.2-C.sub.20 acyloxy, C.sub.3-C.sub.20 alkyl diketonate, C.sub.6-C.sub.24 aryl diketonate, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkylsulfonato, C.sub.5-C.sub.20 arylsulfonato, C.sub.1-C.sub.20 alkylsulfanyl, C.sub.5-C.sub.20 arylsulfanyl, C.sub.1-C.sub.20 alkylsulfinyl, and C.sub.5-C.sub.20 arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, and C.sub.5-C.sub.20 aryl.

    9. The catalysts according to claim 1, wherein X.sup.1 and A.sup.1 may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

    10. The catalysts according to claim 1, wherein L.sup.1 and X.sup.1 may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

    11. The catalysts according to claim 1, wherein in a preferred embodiment, X.sup.1 denotes a halogen, in particular, fluorine, chlorine, bromine or iodine, nitrate, benzoate, C.sub.1-C.sub.5 carboxylate, C.sub.1-C.sub.5 alkyl, phenoxy, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.5 alkylthiol, C.sub.6-C.sub.24 arylthiol, C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.5 alkyl sulfonate.

    12. The catalysts according to claim 1, wherein in a particularly preferred embodiment, X.sup.1 is chlorine, nitrate, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), C.sub.6F.sub.5O (pentafluorophenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH.sub.3C.sub.6H.sub.4SO.sub.3), mesylate (2,4,6-trimethylphenyl) or CF.sub.3SO.sub.3 (trifluoromethanesulfonate).

    13. The catalysts according to claim 1, wherein R.sup.1-R.sup.6 are identical or different and represent hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R.sup.1-R.sup.6, except that R.sup.2 does not represent phenyl when R.sup.1R.sup.3R.sup.4R.sup.5R.sup.6H; or alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures.

    14. The catalysts according to claim 1, wherein R, R, R, R and R are identical or different and represent hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkylsilyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R, R, R, R and R, wherein alternatively in each case two directly adjacent radicals from the group of R, R, R, R and R, including the atoms to which they are attached, generating one or more cyclic structures, including aromatic structures; R.sup.C1 and R.sup.C2 are identical or different and are as defined for R, R, R and R.

    15. Group 8 transition metal catalysts having general structures of formulas (VII): ##STR00078## wherein M is a Group 8 transition metal; X.sup.1 preferably represents an anionic ligand; L.sup.1 and L.sup.2 are identical or different and represent two ligands, preferably neutral electron donor ligands; L.sup.1 and X.sup.1 may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; R.sup.1-R.sup.6 are identical or different and selected from hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, except that R.sup.2 does not represent phenyl when R.sup.1=R.sup.3R.sup.4R.sup.5R.sup.6H; wherein alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures; A.sup.1, T.sup.1, C.sup.1-C.sup.2, R, R, R and R, R.sup.C1 and R.sup.C2 are as defined in claim 2-14; A.sup.1 and X.sup.1 may be joined to form a dianionic ligand and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; wherein the ring G is a 4-, 5-, 6-, 7-, 8-, 9- or 10-membered ring, and Z is a linking group comprising from one to seven linked vertex atoms selected from the group comprising C, O, N, P, S and Si with available valences optionally occupied by hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkylsilyl or alkoxysilyl, where these vertex atoms may each optionally all be substituted by one or more aforementioned groups defined for R, R, R and R; or alternatively in each case two directly adjacent vertex atoms from Z generate one or more cyclic structures, including aromatic structures.

    16. The catalysts according to claim 15, wherein M is Ru or Os.

    17. The catalysts according to claim 15, wherein L.sup.1 is selected from phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, phosphite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, pyrazine, thiocarbonyl, thioether, triazole carbene, N-Heterocyclic carbene, substituted NHC, and a cyclic alkyl amino carbene; or wherein L.sup.1 represent a phosphine ligand having the formula P(Q.sup.1).sub.3 with Q.sup.1 are identical or different and are alkyl, preferably C.sub.1-C.sub.10 alkyl, more preferably C.sub.1-C.sub.5-alkyl, cycloalkyl-, preferably C.sub.3-C.sub.20 cycloalkyl, more preferably C.sub.3-C.sub.8 cycloalkyl, preferably cyclopentyl, cyclohexyl, and neopentyl, aryl, preferably C.sub.6-C.sub.24 aryl, more preferably phenyl or toluyl, alkyl-phosphabicyclononane, C.sub.3-C.sub.20 cycloalkyl phospha-bicyclononane, a sulfonated phosphine ligand of formula P(Q.sup.2).sub.3 wherein Q.sup.2 represents a mono- or poly-sulfonated Q.sup.1-ligand; C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10-alkyl-phosphinite ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl phosphonite ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl phosphite-ligand, a C.sub.6-C.sub.24aryl C.sub.1-C.sub.10 alkyl arsine ligand, a C.sub.6-C.sub.24aryl or C.sub.1-C.sub.10 alkyl amine ligands, a pyridine ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl-sulfoxide ligand, a C.sub.6-C.sub.24-aryl or C.sub.1-C.sub.10 alkyl ether ligand or a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl amide ligands which all can be multiply substituted, for example by a phenyl group, wherein these substituents are in turn optionally substituted by one or more halogen, C.sub.1-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy radicals; or wherein L.sup.1 represent a pyridine ligand which in this application is a generic term and include all the unsubstituted and substituted nitrogen-containing ligands described in WO-A-03/011455 and U.S. Pat. No. 6,759,537 B2; examples are: pyridine, picolines (-, -, and -picoline), lutidines (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 (2-, 3- and 4-chloropyridine), bromopyridines (2-, 3- and 4-bromopyridine), nitropyridines (2-, 3- and 4-nitropyridine), bipyridine, picolylimine, gamma-pyran, phenanthroline, pyrimidine, bipyrimide, pyrazine, indole, coumarine, carbazole, pyrazole, pyrrole, imidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine benzimidazole, bisimidazole, bisoxazole pyrrole, imidazole and phenylimidazole; or wherein L.sup.1 represent a N-Heterocyclic carbene (NHC) having a general structure of the formulas (IIIa) or (IIIb), ##STR00079## wherein R.sup.7-R.sup.14, R.sup.11, R.sup.12 are identical or different and are hydrogen, straight or branched C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy, C.sub.2-C.sub.20, alkynyloxy, C.sub.6-C.sub.20 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio, C.sub.6-C.sub.20 arylthio, C.sub.1-C.sub.20 alkylsulfonyl, C.sub.1-C.sub.20 alkyl sulfonate, C.sub.6-C.sub.20 aryl sulfonate or C.sub.1-C.sub.20 alkyl sulfinyl, and one or more of the radicals R.sup.7-R.sup.14, R.sup.11, R.sup.12 can independently of one another be substituted by one or more substituents, preferably straight or branched C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.10 alkoxy or C.sub.6-C.sub.24 aryl, where these aforementioned substituents may in turn be substituted by one or more radicals, preferably selected from the group comprising halogen, especially chlorine or bromine, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy and phenyl; or wherein L.sup.1 represent a cyclic alkyl amino carbenes (CAACs) having a general structure of the Formula (VI): ##STR00080## wherein the ring A is a 4-, 5-, 6-, or 7-membered ring, and Z is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S and Si with available valences optionally occupied by hydrogen, oxo or R-substituents, wherein R is independently selected from the group comprising C.sub.1 to C.sub.12 hydrocarbyl groups, substituted C.sub.1 to C.sub.12 hydrocarbyl groups, and halides, and each R.sup.15 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluyl, chlorophenyl, phenol, or substituted phenol.

    18. The catalysts according to claim 15, wherein X.sup.1 is selected from hydrogen, halogen, nitrate, pseudohalogen, straight-chain or branched C.sub.1-C.sub.30-alkyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 alkylthiol, C.sub.6-C.sub.24 arylthiol, C.sub.1-C.sub.20 alkoxy, C.sub.6-C.sub.24 aryloxy, C.sub.2-C.sub.24 alkoxycarbonyl, C.sub.6-C.sub.20 aryloxycarbonyl, C.sub.2-C.sub.20 acyl, C.sub.2-C.sub.20 acyloxy, C.sub.3-C.sub.20 alkyl diketonate, C.sub.6-C.sub.24 aryl diketonate, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkylsulfonato, C.sub.5-C.sub.20 arylsulfonato, C.sub.1-C.sub.20 alkylsulfanyl, C.sub.5-C.sub.20 arylsulfanyl, C.sub.1-C.sub.20 alkylsulfinyl, and C.sub.5-C.sub.20 arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, and C.sub.5-C.sub.20 aryl; or wherein X.sup.1 and A.sup.1 may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; or wherein L.sup.1 and X.sup.1 may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; or wherein in a preferred embodiment, X.sup.1 denotes a halogen, in particular, fluorine, chlorine, bromine or iodine, nitrate, benzoate, C.sub.1-C.sub.5carboxylate, C.sub.1-C.sub.5 alkyl, phenoxy, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.5 alkylthiol, C.sub.6-C.sub.24 arylthiol, C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.5 alkyl sulfonate; or wherein in a particularly preferred embodiment, X.sup.1 is chlorine, nitrate, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), C.sub.6F.sub.5O (pentafluorophenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH.sub.3C.sub.6H.sub.4SO.sub.3), mesylate (2,4,6-trimethylphenyl) or CF.sub.3SO.sub.3 (trifluoromethanesulfonate).

    19. The catalysts according to claim 15, wherein R.sup.1-R.sup.6 are identical or different and represent hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R.sup.1-R.sup.6, except that R.sup.2 does not represent phenyl when R.sup.1R.sup.3R.sup.4R.sup.5R.sup.6H; or alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures.

    20. A supported catalyst comprising the catalysts according to claim 1 and a support.

    21. The supported catalyst according to claim 20 wherein the carrier is selected from the group consisting of porous inorganic solids, such as amorphous or paracrystalline materials, crystalline molecular sieves and modified layered materials including one or more inorganic oxides and organic polymers as well as carbon, carbon nanotubes, graphene, Metal organic frameworks and cross-linked, reticular polymeric resins, such as functionalized cross-linked polystyrenes, e.g., chloromethyl-functionalized cross-linked polystyrenes; the catalysts can be deposited onto the support by, impregnation, ion-exchange, deposition-precipitation, - interactions and vapor deposition; alternatively, the catalysts are chemically bound to the support via one or more covalent chemical bonds.

    22. A method for making metal catalysts (I-II) or (VII) according to claim 1 comprising contacting a precursor compound of the formula (X.sup.1X.sup.2ML.sub.3) or (X.sup.1X.sup.2ML.sub.4) with an acetylenic compound, and at least one ditopic or multitopic ligand; wherein for the precursor compound, M is a Group 8 transition metal; X.sup.1 and X.sup.2 are identical or different and represent two ligands, preferably anionic ligands; and L represents neutral electron donor ligands.

    23. The method according to claim 22, wherein the acetylenic compound having the general formula (VIII) ##STR00081## wherein D is a leaving group; R.sup.16 to R.sup.17 are as defined below; R.sup.16 is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R.sup.16 is aryl, polyaryl, or heteroaryl, R.sup.16 may be substituted with any combination of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 and can be linked with any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 to form one or more cyclic aromatic or non-aromatic groups; R.sup.17 is selected from annulenes, having the general formula C.sub.nH.sub.n (when n is an even number) or C.sub.nH.sub.n+1 (when n is an odd number); well-know representative compounds of annulenes, but not limited, are cyclobutadiene, benzene, and cyclooctatetraene; annulenes can be aromatic or anti-aromatic; every H-atom from the annulene fragment can be substituted by halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R.sup.17 is aryl, polyaryl, or heteroaryl, R.sup.17 may be substituted with any combination of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and can be linked with any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 to form one or more cyclic aromatic or non-aromatic groups.

    24. The method according to claim 22, wherein the method comprising: the first step: contacting X.sup.1X.sup.2ML.sub.3 or X.sup.1X.sup.2ML.sub.4 and the acetylenic compound in a molar ratio between 1 to 20 are added to a mixture of acid/solvent; heating the mixture between 40 C. and 200 C. for a time less than 10 hours; removing the solvent and adding a non-polar solvent; filtering and washing the resulting precipitation using the same non-polar solvent; after drying, a modified indenylidene complex is obtained; the second step: treating a solution of the ditopic or multitopic ligand in a suitable solvent with the non-chelating modified indenylidene complex in a required molar ratio and adding a required amount of silver for a time sufficient to effectuate the ligand exchange, at a suitable temperature typically between ambient and 80 C. to yield the desired modified indenylidene catalyst compound; the reaction temperature was then lowered to room temperature, the by-product and excess of silver was removed by filtration and the filtrate was concentrated under reduced pressure; the isolated solid residue provides the desired product having structure I or II or VII.

    25. A method for making metal catalysts (I-II) or (VII) according to claim 1 comprising: the first step: contacting X.sup.1X.sup.2ML.sub.3 or X.sup.1X.sup.2ML.sub.4 and the acetylenic compound in a molar ratio between 1 to 20 are added to a mixture of acid/solvent; heating the mixture between 40 C. and 200 C. for a time less than 10 hours; removing the solvent and adding a non-polar solvent; filtering and washing the resulting precipitation using the same non-polar solvent; after drying, a modified indenylidene complex is obtained; the modified indenylidene complex is 1.sup.st generation compound or 2.sup.nd generation compound produced by mixing the 1.sup.st generation compound and the preferred NHC or CAAC ligand in a suitable solvent for a time sufficient to effectuate the ligand exchange, or 3.sup.rd generation compound produced by mixing the 2.sup.nd generation compound and the preferred pyridine ligand as solvent, for a time sufficient to effectuate the phosphine ligand exchange; the second step: treating a solution of the ditopic or multitopic ligand in a suitable solvent with the modified indenylidene complex in a required molar ratio and adding a required amount of silver for a time sufficient to effectuate the ligand exchange, at a suitable temperature typically between ambient and 80 C. to yield the desired modified indenylidene catalyst compound; the reaction temperature was then lowered to room temperature, the by-product and excess of silver was removed by filtration and the filtrate was concentrated under reduced pressure; the isolated solid residue provides the desired product having structure I or II or VII.

    26. The method according to claim 25, wherein the molar ratio of X.sup.1X.sup.2ML.sub.3 or X.sup.1X.sup.2ML.sub.4 and the acetylenic compound is between 1 to 15, more preferable between 1 to 10, most preferable between 1 to 5.

    27. The method according to claim 25, wherein the acid of acid/solvent in the first step is preferable a Brnsted or a Lewis acid; in case of a Brnsted acid more preferable from the HX group, the HX group is HF, HCl, HBr, or HI, most preferable HCl or HBr; In case of a Lewis acid more preferable a Lewis acid based on Si, Al or Ti, most preferable having the structure M.sup.aX.sub.3-yR.sup.a.sub.y in case of Si and Ti and M.sup.aX.sub.2-yR.sup.a.sub.y in case of Al; the acid concentration in the solvent is lower than 5 mol/L, preferable lower than 1 mol/L, more preferable lower than 0.5 mol/L, and most preferable lower than 0.3 mol/L.

    28. The method according to claim 25, wherein heating the mixture between 50 C. and 150 C., most preferable between 60 C. and 100 C. for a time less than 8 hours, more preferable less than 5 hours, most preferable less than 3 hours in the first step.

    29. Use of the metal catalysts according to claim 1 in olefin and alkyne metathesis reactions, especially for ring-closing metathesis (RCM), cross metathesis (CM), ring-opening metathesis (ROM), ring-opening metathesis polymerization (ROMP), cyclic diene metathesis (ADMET), self-metathesis, reaction of alkenes and alkynes, polymerization of alkynes and the olefination of carbonyls in neat conditions, in the presence of protic solvents, polar aprotic or non-polar solvents.

    30. A process to produce alpha-olefin comprising contacting an unsaturated fatty acid with an alkene and the catalysts according to claim 1 wherein the alpha olefin produced has at least one more carbon atom than the alkene.

    31. A process to produce alpha-olefin comprising contacting an unsaturated fatty acid ester and or unsaturated fatty acid alkyl ester with an alkene and the catalysts according to claim 1 wherein the alpha olefin produced has at least one more carbon atom than the alkene.

    32. An activation method comprising: bringing the catalysts according to claim 1 into contact with an activator under conditions such that said activator is able to at least partly cleave a bond between the metal and the at least one ditopic/multitopic ligand of the catalysts.

    33. The method according to claim 32, wherein the activator is selected from Brnsted acids, preferable the nature of the Brnsted acid can be liquid, solid, inorganic or organic, more preferable a liquid, most preferable selected HCl, HBr, H.sub.2SO.sub.4, CH.sub.3COOH, and sulphonic acid resins.

    34. The method according to claim 32, wherein the activator is a Lewis acid which can be selected from the group consisting of: M.sup.a(I) halides, compounds represented by the formula M.sup.aX.sub.2-yR.sup.a.sub.y (0y2), wherein R.sup.a is equal to R.sup.1-R.sup.6 defined as herein-above, X is atom of the halogen group and identical or different in case more then one halogen atom is present, and M.sup.a is an atom having an atomic mass from 27 to 124 and being selected from the group consisting of groups IB, IIB, IIIA, IVB, IVA and VA of the Periodic Table of elements under conditions such that at least partial cleavage of a bond between the metal and the ditopic or multitopic ligand of the catalysts occurs. compounds represented by the formula M.sup.aX.sub.3-yR.sup.a.sub.y (0y3) wherein R.sup.a, X and M.sup.a defined as herein-above; compounds represented by the formula M.sup.aX.sub.4-yR.sup.a.sub.y (0y4) wherein R.sup.a, X and M.sup.a defined as herein-above; compounds represented by the formula M.sup.aX.sub.5-yR.sup.a.sub.y (0y5) wherein R.sup.a, X and M.sup.a defined as herein-above; compounds represented by the formula M.sup.aX.sub.6-yR.sup.a.sub.y (0y6) wherein R.sup.a, X and M.sup.a defined as herein-above.

    35. An activation method comprising: bringing the catalysts according to claim 1 into contact with an acid wherein the acid is an acid generated in situ from bringing into contact a molecule of the formula RYH with a Lewis acid which at least contains one halogen atom or from a photo-acid generator under conditions such that acid is able to at least partly cleave a bond between the metal and said at least one ditopic/multitopic ligand; wherein Y is selected from the group consisting of oxygen, sulphur and selenium, and R as defined hereinabove.

    36. The method according to claim 35, wherein the conditions include: a molar ratio between the acid and the catalysts being above 0.2 and below 80; a contact time from 2 seconds to 150 hours; a contact temperature from about 100 C. to about +100 C.

    37. A process to produce polymers or thermoset networks by combining a mixture A containing a cyclic olefin or a mixture of cyclic olefins and a catalyst of the formula (I or II or VII) and a mixture B containing a cyclic olefin or a mixture of cyclic olefins and an activator as defined in claim 32 to be applied in casting processes, reaction-injection molding (RIM) processes, resin transfer molding (RTM) processes, vacuum infusion and vacuum forming processes and reactive rotational molding (RRM) processes.

    38. A process to produce polymers or thermoset networks by combining a mixture A containing a cyclic olefin or a mixture of cyclic olefins and a catalyst of the formula (I or II or VII) and a mixture B containing a cyclic olefin or a mixture of cyclic olefins and an activator as defined in claim 35 to be applied in casting processes, reaction-injection molding (RIM) processes, resin transfer molding (RTM) processes, vacuum infusion and vacuum forming processes and reactive rotational molding (RRM) processes, wherein the catalyst of the formula VII is: ##STR00082## wherein M is a group 8 transition metal; X.sup.1 preferably represents an anionic ligand; L.sup.1 and L.sup.2 are identical or different and represent two ligands, preferably neutral electron donor ligands; L.sup.1 and X.sup.1 may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; R.sup.1-R.sup.6 are identical or different and selected from hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, except that R.sup.2 does not represent phenyl when R.sup.1R.sup.3R.sup.4R.sup.5R.sup.6H; wherein alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures; A.sup.1, T.sup.1, C.sup.1-C.sup.2, R, R, R and R, R.sup.C1 and R.sup.C2 are as defined in claim 2-14; A.sup.1 and X.sup.1 may be joined to form a dianionic ligand and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; wherein the ring G is a 4-, 5-, 6-, 7-, 8-, 9- or 10-membered ring, and Z is a linking group comprising from one to seven linked vertex atoms selected from the group comprising C, O, N, P, S and Si with available valences optionally occupied by hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkylsilyl or alkoxysilyl, where these vertex atoms may each optionally all be substituted by one or more aforementioned groups defined for R, R, R and R; or alternatively in each case two directly adjacent vertex atoms from Z generate one or more cyclic structures, including aromatic structures.

    Description

    BRIEF DESCRIPTION OF THE FIGURES

    [0085] FIG. 1 is reaction progress after 1 h during the synthesis of catalyst 12.

    [0086] FIG. 2 is reaction progress after 5 h during the synthesis of catalyst 12.

    [0087] FIG. 3 is comparison between commercial catalyst N and 5A, 6A and 7A of this invention for the ring closing metathesis (RCM) of diethyldiallylmalonate (DEDAM) using activation.

    [0088] FIG. 4 is comparison between catalyst F and 5A-7A at a 0.1 mol % loading for the RCM of DEDAM.

    [0089] FIG. 5 is influence of activator amount on the catalytic performance for RCM of DEDAM.

    [0090] FIG. 6 is ROMP of DCPD using catalyst 4A, 8A, 9A and 12 of this invention.

    [0091] FIG. 7 is ROMP of DCPD using in-situ activation.

    DETAILED DESCRIPTION

    Terminology and Definitions

    [0092] Unless otherwise mentioned, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

    [0093] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

    [0094] The term alkyl as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term C.sub.1-C.sub.6-alkyl intends an alkyl group of 1 to 6 carbon atoms, and the specific term cycloalkyl intends a cyclic alkyl group, typically having 3 to 8 carbon atoms.

    [0095] The term substituted alkyl refers to alkyl substituted with one or more substituent groups, and the terms heteroatom-containing alkyl and heteroalkyl refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the term alkyl includes linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl.

    [0096] The term alkylene as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where alkyl is as defined above.

    [0097] The term alkenyl as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, and the like. Preferred alkenyl groups herein contain 2 to about 12 carbon atoms. The term cycloalkenyl intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term substituted alkenyl refers to alkenyl substituted with one or more substituent groups, and the terms heteroatom-containing alkenyl and heteroalkenyl refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the term alkenyl include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl.

    [0098] The term alkenylene as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where alkenyl is as defined above.

    [0099] The term alkynyl as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term substituted alkynyl refers to alkynyl substituted with one or more substituent groups, and the terms heteroatom-containing alkynyl and heteroalkynyl refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the term alkynyl include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl respectively.

    [0100] The term alkoxy as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an alkoxy group may be represented as O-alkyl where alkyl is as defined above. Analogously, alkenyloxy refers to an alkenyl group bound through a single, terminal ether linkage, and alkynyloxy refers to an alkynyl group bound through a single, terminal ether linkage.

    [0101] The term aryl as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. Substituted aryl refers to an aryl moiety substituted with one or more substituent groups, and the terms heteroatom-containing aryl and heteroaryl refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

    [0102] The term aryloxy as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein aryl is as defined above. An aryloxy group may be represented as O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxyphenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

    [0103] The term alkaryl refers to an aryl group with an alkyl substituent, and the term aralkyl refers to an alkyl group with an aryl substituent, wherein aryl and alkyl are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms. Alkaryl groups include, but not limit to, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms alkaryloxy and aralkyloxy refer to substituents of the formula OR wherein R is alkaryl or aralkyl, respectively, as just defined.

    [0104] The term acyl refers to substituents having the formula (CO)-alkyl, (CO)-aryl, or (CO)-aralkyl, and the term acyloxy refers to substituents having the formula O(CO)-alkyl, O(CO)aryl, or O(CO)-aralkyl, wherein alkyl, aryl, and aralkyl are as defined above.

    [0105] The terms cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.

    [0106] The terms halo and halogen are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

    [0107] Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term hydrocarbylene intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups, and the terms heteroatom-containing hydrocarbyl and heterohydrocarbyl refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups, and the terms heteroatom containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.

    [0108] The term heteroatom-containing as in a heteroatom-containing hydrocarbyl group refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term heteroalkyl refers to an alkyl substituent that is heteroatom-containing, the term heterocyclic refers to a cyclic substituent that is heteroatom-containing, the terms heteroaryl and heteroaromatic respectively refer to aryl and aromatic substituents that are heteroatom-containing, and the like. It should be noted that a heterocyclic group or compound may or may not be aromatic, and further that heterocycles may be monocyclic, bicyclic, or polycyclic as described above with respect to the term aryl. Examples of heteroalkyl groups include alkoxyalkyl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, 1,2,3 triazolyl, tetrazolyl, etc., and examples of heteroatom containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, etc.

    [0109] By substituted as in substituted hydrocarbyl, substituted alkyl, substituted aryl, and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy, C.sub.2-C.sub.24 alkenyloxy, C.sub.2-C.sub.24 alkynyloxy, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy, C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2C.sub.24 alkylcarbonyl (CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl (CO-aryl)), acyloxy (O-acyl, including C.sub.2C.sub.24 alkylcarbonyloxy (OCO-alkyl) and C.sub.6-C.sub.24 arylcarbonyloxy (OCO-aryl)), C.sub.2C.sub.24 alkoxycarbonyl ((CO)O alkyl), C.sub.6-C.sub.24 aryloxycarbonyl ((CO)O-aryl), halocarbonyl (CO)X where X is halo), C.sub.2-C.sub.24 alkylcarbonato (O(CO)O-alkyl), C.sub.6-C.sub.24 arylcarbonato (O(CO)O-aryl), carboxy (COOH), carboxylato (COO.sup.), carbamoyl ((CO)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl) substituted carbamoyl ((CO)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl ((CO)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl ((CO)NH-aryl), di-(C.sub.5-C.sub.24 aryl) substituted carbamoyl ((CO)N(C.sub.5-C.sub.24 aryl).sub.2), M(C.sub.1-C.sub.24 alkyl) (C.sub.5-C.sub.24 aryl))-substituted carbamoyl, thiocarbamoyl ((CS)NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl ((CS)N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl ((CS)N(C.sub.5-C.sub.24 aryl).sub.2), N(C.sub.1-C.sub.24 alkyl)N(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl, carbamido (NH(CO)NH.sub.2), cyano (CN), cyanato (OCN), thiocyanato (SCN), formyl ((CO)H), thioformyl ((CS)H), amino (NH.sub.2), mono-(C.sub.1-C.sub.24 alkyl)-substituted amino, di-(C.sub.1-C.sub.24 alkyl) substituted amino, mono-(C.sub.5-C.sub.24 aryl)-substituted amino, di-(C.sub.5-C.sub.24 aryl)-substituted amino, C.sub.2-C.sub.24 alkylamido (NH(CO)-alkyl), C.sub.6-C.sub.24 arylamido (NH(CO)-aryl), imino (CRNH where R=hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (CRN(alkyl), where R=hydrogen, C.sub.1-C.sub.24 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), arylimino (CRN(aryl), where R=hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 aralkyl, etc.), nitro (NO.sub.2), nitroso (NO), sulfo (SO.sub.2OH), sulfonato (SO.sub.2O.sup.), C.sub.1-C.sub.24 alkylsulfanyl (S-alkyl; also termed alkylthio), C.sub.5-C.sub.24 arylsulfanyl (S-aryl; also termed arylthio), C.sub.1-C.sub.24 alkylsulfinyl ((SO)-alkyl), C.sub.5-C.sub.24 arylsulfinyl ((SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl (SO.sub.2-alkyl), C.sub.5-C.sub.24 arylsulfonyl (SO.sub.2-aryl), boryl (BH.sub.2), borono (B(OH).sub.2), boronato (B(OR).sub.2 where R is alkyl or other hydrocarbyl), phosphono (P(O)(OH).sub.2), phosphonato (P(O)(O).sub.2), phosphinato (P(O)(O.sup.)), phosphor (PO.sub.2), and phosphino (PH.sub.2); and the hydrocarbyl moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl, more preferably C.sub.1-C.sub.6 alkyl), C.sub.2-C.sub.24 alkenyl (preferably C.sub.2-C.sub.12 alkenyl, more preferably C.sub.2-C.sub.6 alkenyl), C.sub.2-C.sub.24 alkynyl (preferably C.sub.2-C.sub.12 alkynyl, more preferably C.sub.2-C.sub.6 alkynyl), C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.24 aryl), C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl).

    [0110] By functionalized as in functionalized hydrocarbyl, functionalized alkyl, functionalized olefin, functionalized cyclic olefin, and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove.

    [0111] In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

    [0112] The present invention comprises a novel family of metathesis catalyst compounds useful for the different types of olefin and alkyne metathesis reactions, including but not limited to Ring closing metathesis (RCM), Cross metathesis (CM), Ring opening metathesis (ROM), Ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET), self-metathesis, conversion of olefins with alkynes (enyne metathesis), polymerization of alkynes, ethylene cross-metathesis and so on.

    ##STR00015##

    [0113] M is a Group 8 metal, preferably ruthenium or osmium,

    [0114] R.sup.1-R.sup.6 are identical or different and represents hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkyl sulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkyl silyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R.sup.1-R.sup.6, and except that R.sup.2 does not represent phenyl when R.sup.1R.sup.3R.sup.4R.sup.5=R.sup.6H;

    [0115] or alternatively in each case two directly adjacent radicals from the group of R.sup.1-R.sup.6, including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures.

    [0116] C.sub.1-C.sub.6 alkyl is, but not limited to, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethyl-propyl and n-hexyl.

    [0117] C.sub.3-C.sub.8 cycloalkyl includes, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

    [0118] C.sub.6-C.sub.24 aryl includes an aromatic radical having 6 to 24 skeletal carbon atoms. Preferred mono-, bi- or tricyclic carbocyclic aromatic radicals have 6 to 10 skeletal carbon atoms, for example but not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

    [0119] X.sup.1 preferably represents an anionic ligand.

    [0120] In the general formulas X.sup.1 can be for example, hydrogen, halogen, pseudohalogen, straight-chain or branched C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.24 aryl, C.sub.1-C.sub.20 alkoxy, C.sub.6-C.sub.24 aryloxy, C.sub.3-C.sub.20 alkyl diketonate, C.sub.6-C.sub.24 aryl diketonate, C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkylsulfonate, C.sub.6-C.sub.24 aryl sulfonate, C.sub.1-C.sub.20 alkyl thiol, C.sub.6-C.sub.24 aryl thiol, C.sub.1-C.sub.20 alkyl sulfonyl or C.sub.1-C.sub.20 alkylsulfinyl-radicals.

    [0121] The abovementioned radical X.sup.1 may further be substituted by one or more additional residues, for example by halogen, preferably fluorine, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20-alkoxy or C.sub.6-C.sub.24 aryl, where these groups may optionally be in turn be substituted by one or more substituents from the group comprising halogen, preferable fluorine, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, and phenyl.

    [0122] L.sup.1 and X.sup.1 may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

    [0123] In a preferred embodiment, X.sup.1 denote halogen, in particular, fluorine, chlorine, bromine or iodine, benzoate, nitrate, C.sub.1-C.sub.5 carboxylate, C.sub.1-C.sub.5 alkyl, phenoxy, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.5 alkyl thiol, C.sub.6-C.sub.24 arylthiol, C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.5 alkyl sulfonate.

    [0124] In a particularly preferred embodiment, X.sup.1 is chlorine, CF.sub.3COO, CH.sub.3COO, CFH.sub.2COO, (CH.sub.3).sub.3CO, nitrate, (CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO (phenoxy), C.sub.6F.sub.5O (pentafluorophenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH.sub.3C.sub.6H.sub.4SO.sub.3), mesylate (2,4,6-trimethylphenyl) or CF.sub.3SO.sub.3 (trifluoromethanesulfonate).

    [0125] A.sup.1-A.sup.2 are identical or different and are selected from the group consisting of oxygen, sulphur, selenium, NR, PR, POR, AsR, AsOR, SbOR and SbR.

    [0126] T.sup.1-T.sup.2 are identical or different and selected from the group consisting of

    ##STR00016##

    [0127] Wherein E preferably represents a donor atom selected from the group consisting of nitrogen, phosphor, oxygen, sulphur, and selenium; wherein for the group

    ##STR00017##

    in case of oxygen, sulphur and selenium, R is omitted for double bonded E or R remains for a single bonded E; wherein for the group

    ##STR00018##

    in case of oxygen, sulphur and selenium, the E-C bound is a single bond and the C atom contains an extra R group or the CR is a double bond or the CR is a double bond.

    [0128] R, R, R, R and R are identical or different and represents hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkyl sulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkyl silyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R, R, R, R and R, wherein alternatively in each case two directly adjacent radicals from the group of R, R, R, R and R, including the atoms to which they are attached, generating one or more cyclic structures, including aromatic structures.

    [0129] C.sub.1-C.sub.6 alkyl is, but not limited to, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethyl-propyl and n-hexyl.

    [0130] C.sub.3-C.sub.8 cycloalkyl includes, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

    [0131] C.sub.6-C.sub.24 aryl includes an aromatic radical having 6 to 24 skeletal carbon atoms. Preferred mono-, bi- or tricyclic carbocyclic aromatic radicals have 6 to 10 skeletal carbon atoms, for example but not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.

    [0132] Alternatively R is optionally substituted with a neutral donor ligand (L.sup.2) as defined by L.sup.1.

    [0133] C.sup.1-C.sup.2 are carbon atoms linked to each other via a single or double bond wherein in case of a single bond each carbon atom bears an extra substituent R.sup.C1 and R.sup.C2.

    [0134] R.sup.C1 and R.sup.C2 are identical or different and are as defined for R, R, R and R.

    [0135] L.sup.1 preferably represent neutral electron donor.

    [0136] The ligand L.sup.1 may, for example, represent a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, phosphite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, pyrazine, thiocarbonyl, thioether, triazole carbene, mesionic carbene (MIC), N-Heterocyclic carbene (NHC), substituted NHC, or cyclic alkyl amino carbene (CAAC) or substituted CAAC.

    [0137] Preferably, ligand L.sup.1 represents a phosphine ligand having the formula P(Q.sup.1).sub.3 with Q.sup.1 are identical or different and are alkyl, preferably C.sub.1-C.sub.10 alkyl, more preferably C.sub.1-C.sub.5-alkyl, cycloalkyl-, preferably C.sub.3-C.sub.20 cycloalkyl, more preferably C.sub.3-C.sub.8 cycloalkyl, preferably cyclopentyl, cyclohexyl, and neopentyl, aryl, preferably C.sub.6-C.sub.24 aryl, more preferably phenyl or toluyl, C.sub.1-C.sub.10 alkyl-phosphabicyclononane, C.sub.3-C.sub.20 cycloalkyl phospha-bicyclononane, a sulfonated phosphine ligand of formula P(Q.sup.2).sub.3 wherein Q.sup.2 represents a mono- or poly-sulfonated Q.sup.1-ligand; C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl-phosphinite ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl phosphonite ligand, a C.sub.6-C.sub.24aryl or C.sub.1-C.sub.10 alkyl phosphite-ligand, a C.sub.6-C.sub.24 aryl C.sub.1-C.sub.10 alkyl arsine ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl amine ligands, a pyridine ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl-sulfoxide ligand, a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl ether ligand or a C.sub.6-C.sub.24 aryl or C.sub.1-C.sub.10 alkyl amide ligands which all can be multiply substituted, for example by a phenyl group, wherein these substituents are in turn optionally substituted by one or more halogen, C.sub.1-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy radicals.

    [0138] The term phosphine includes, for example, PPh.sub.3, P(p-Tol).sub.3, P(o-Tol), PPh(CH.sub.3).sub.2, P(CF.sub.3).sub.3, P(p-FC.sub.6H.sub.4).sub.3, P(p-CF.sub.3C.sub.6H.sub.4).sub.3, P(C.sub.6H.sub.4SO.sub.3Na).sub.3, P(CH.sub.2C.sub.6H.sub.4SO.sub.3Na).sub.3, P(iso-Propyl).sub.3, P(CHCH.sub.3(CH.sub.2CH.sub.3)).sub.3, P(cyclopentyl).sub.3, P(cyclohexyl).sub.3, P(Neopentyl).sub.3 and cyclohexyl-phosphabicyclononane.

    [0139] The term phosphinite includes for example triphenylphosphinite, tricyclohexylphosphinite, triisopropylphosphinite and methyldiphenylphosphinite.

    [0140] The term phosphite includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyldiphenylphosphite.

    [0141] The term stibine includes, for example triphenylstibine, tricyclohexylstibine and Trimethylstibene.

    [0142] The term sulfonate includes, for example, trifluoromethanesulfonate, tosylate and mesylate.

    [0143] The term sulfoxide includes, for example, CH.sub.3S(O)CH.sub.3 and (C.sub.6H.sub.5).sub.2SO.

    [0144] The term thioether includes, for example CH.sub.3SCH.sub.3, C.sub.6H.sub.5SCH.sub.3, CH.sub.3OCH.sub.2CH.sub.2SCH.sub.3 and tetra-hydrothiophene.

    [0145] The term pyridine in this application is a generic term and includes all the unsubstituted and substituted nitrogen-containing ligands described in WO-A-03/011455 and U.S. Pat. No. 6,759,537 B2. Examples are: pyridine, picolines (-, -, and -picoline), lutidines (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 (2-, 3- and 4-chloropyridine), bromopyridines (2-, 3- and 4-bromopyridine), nitropyridines (2-, 3- and 4-nitropyridine), bipyridine, picolylimine, gamma-pyran, phenanthroline, pyrimidine, bipyrimide, pyrazine, indole, coumarine, carbazole, pyrazole, pyrrole, imidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine benzimidazole, bisimidazole, bisoxazole, pyrrole, imidazole and phenylimidazole.

    [0146] In other useful embodiment ligand L.sup.1 represents a N-Heterocyclic carbene (NHC) usually having a structure of the formulas (IIIa) or (IIIb):

    ##STR00019##

    [0147] by which

    [0148] R.sup.7-R.sup.14, R.sup.11, R.sup.12 are identical or different and are hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylammonium, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for R.sup.1-R.sup.6.

    [0149] Optionally, one or more of the radicals R.sup.7-R.sup.14, R.sup.11, R.sup.12 independently of one another can be substituted by one or more substituents, preferably straight or branched C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.10 alkoxy or C.sub.6-C.sub.24 aryl, where these aforementioned substituents may in turn be substituted by one or more radicals, preferably selected from the group comprising halogen, especially chlorine or bromine, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy and phenyl.

    [0150] Just for clarification, the depicted structures of the N-Heterocyclic carbene in the general formulas (IIIa) and (IIIb) are equal with the N-Heterocyclic carbenes described in the literature, where frequently the structures (IIIa) and (IIIb) are used, which highlighting the carbene character of N-Heterocyclic carbene. This also applies to the corresponding preferred, structures shown below (IVa)-(IVf)

    ##STR00020##

    [0151] In a preferred embodiment of the catalysts the general formulas (IIIa) and (IIIb) R.sup.7, R.sup.8, R.sup.11, R.sup.11 R.sup.12 and R.sup.12 are independently of one another denote hydrogen, C.sub.6-C.sub.24-aryl, particularly preferably phenyl, straight or branched C.sub.1-C.sub.10 alkyl, particularly preferably propyl or butyl, or together with the inclusion of the carbon atoms to which they are attached form a cycloalkyl or aryl radical, where all the abovementioned radicals are optionally substituted may be substituted by one or more further radicals selected from the group comprising straight or branched C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.24 aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

    [0152] In a particularly preferred embodiment, the catalysts of the general formulas (I-II) have one N-Heterocyclic carbene (NHC) as ligand L.sup.1, where the radicals R.sup.9, R.sup.10, R.sup.13 and R.sup.14 are identical or different and are straight or branched C.sub.1-C.sub.10 alkyl, particularly preferably i-propyl or neopentyl, C.sub.3-C.sub.10 cycloalkyl, preferably adamantyl, C.sub.6-C.sub.24 aryl, particularly preferably phenyl, C.sub.1-C.sub.10 alkylsulfonate, particularly preferably methanesulphonate, C.sub.1-C.sub.10 aryl sulphonate, particularly preferably p-toluenesulfonate.

    [0153] If necessary, the above-mentioned residues are substituted as the meanings of R.sup.9, R.sup.10, R.sup.13 and R.sup.14 by one or more further radicals selected from the group comprising straight or branched C.sub.1-C.sub.5 alkyl, especially methyl, C.sub.1-C.sub.5 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, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

    [0154] In particular, the radicals R.sup.9, R.sup.10, R.sup.13 and R.sup.14 can be identical or different and denote i-propyl, neopentyl, adamantyl, mesityl or 2,6-diisopropylphenyl.

    [0155] Particularly preferred N-Heterocyclic carbenes (NHC) have the following structure (IVa)-(IVf), in which Mes stands for a 2,4,6-trimethylphenyl radical or alternatively, in all cases, for a 2,6-diisopropylphenyl radical.

    ##STR00021##

    [0156] In alternative embodiment, the neutral ligand L may be selected from a ligand of any of the formulas (Va-Vc):

    ##STR00022##

    [0157] R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.11, R.sup.12, R.sup.13, R.sup.14 are identical or different and are equal to R.sup.3-R.sup.6 defined as herein-above. Any adjacent group of R.sup.11, R.sup.11 and R.sup.12 in structure (Vb) and (Vc) may form a 3, 4, 5, 6, or 7 membered cycloalkyl, alkylene bridge, or aryl.

    [0158] In other useful embodiments, one of the N groups bound to the carbene in Formula (IIIa) or (IIIb) is replaced with another heteroatom, preferably S, O or P, preferably an S heteroatom. Other useful N-heterocyclic carbenes include the compounds described in Chem. Eur. J 1996, 2, 772 and 1627; Angew. Chem. Int. Ed. 1995, 34, 1021; Angew. Chem. Int. Ed. 1996, 35, 1121; and Chem. Rev. 2000, 100, 39.

    [0159] For purposes of this invention and claims thereto, cyclic alkyl amino carbenes (CAACs) are represented by the Formula (VI):

    ##STR00023##

    [0160] Wherein the ring A is a 4-, 5-, 6-, or 7-membered ring, and Z is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S and Si with available valences optionally occupied by hydrogen, oxo or R-substituents, wherein R is independently selected from the group comprising C.sub.1 to C.sub.12 hydrocarbyl groups, substituted C.sub.1 to C.sub.12 hydrocarbyl groups, and halides, and each R.sup.15 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluyl, chlorophenyl, phenol, or substituted phenol.

    [0161] Some particularly useful CAACs include:

    ##STR00024##

    [0162] Other useful CAACs include the compounds described in U.S. Pat. No. 7,312,331 and in Angew. Chem. Int. Ed. 2005, 44, 7236-7239.

    [0163] For the case that the R group present in T.sup.1 or T.sup.2 of the inventive catalysts with the general formula (I) is further substituted with a neutral donor ligand, the following examples can be generated with the structures of the general formula (VII).

    ##STR00025##

    [0164] Wherein the ring G is a 4-, 5-, 6-, 7-, 8-, 9- or 10-membered ring, and Z is a linking group comprising from one to seven linked vertex atoms selected from the group comprising C, O, N, P, S and Si with available valences optionally occupied by hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF.sub.3, nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, sulphonate (SO.sub.3.sup.), OSO.sub.3.sup., PO.sub.3.sup. or OPO.sub.3.sup., acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylamino-, alkylthio-, arylthio, alkyl sulfonyl, alkylsulfinyl, dialkylamino, alkylammonium, alkylsilyl or alkoxysilyl, where these vertex atoms may each optionally all be substituted by one or more aforementioned groups defined for R, R, R and R,

    [0165] or alternatively in each case two directly adjacent vertex atoms from Z generate one or more cyclic structures, including aromatic structures.

    [0166] L.sup.1 and L.sup.2 are identical or different ligands, preferably represent neutral electron donors, and L.sup.2 has the same meaning as L.sup.1 as defined in structures (I-II)

    [0167] wherein M, X.sup.1, A.sup.1, T.sup.1, L.sup.1, R.sup.1-R.sup.6 and R, R, R and R have the same meanings as defined in the general structures (I-II).

    [0168] As examples of the catalysts of the invention, the following structures may be mentioned:

    ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##

    [0169] In certain embodiments, the catalyst compound employed in the olefin metathesis processes may be bound to or deposited on a solid catalyst support. The solid catalyst support will make the catalyst compound heterogeneous, which will simplify catalyst recovery. In addition, the catalyst support may increase catalyst strength and attrition resistance. Suitable catalyst supports include, without limitation, silica's, alumina's, silica-alumina's, aluminosilicates, including zeolites and other crystalline porous aluminosilicates; as well as titania's, zirconia, magnesium oxide, carbon, carbon nanotubes, graphene, Metal organic frameworks and cross-linked, reticular polymeric resins, such as functionalized cross-linked polystyrenes, e.g., chloromethyl-functionalized cross-linked polystyrenes.

    [0170] The catalyst compound may be deposited onto the support by any method known to those skilled in the art, including, for example, impregnation, ion-exchange, deposition-precipitation, II-II interactions and vapor deposition. Alternatively, the catalyst compound may be chemically bound to the support via one or more covalent chemical bonds, for example, the catalyst compound may be immobilized by one or more covalent bonds with one or more of substituents of the indenylidene ligand or directly immobilized via one or more chemical bounds on the Group 8 metal by substituting one or more anionic ligands or immobilized via one or more chemical bounds between the ligand and the support.

    [0171] If a catalyst support is used, the catalyst compound may be loaded onto the catalyst support in any amount, provided that the metathesis process proceeds to the desired metathesis products. Generally, the catalyst compound is loaded onto the support in an amount that is greater than about 0.01 wt % of the Group 8 metal, based on the total weight of the catalyst compound plus support. Generally, the catalyst compound is loaded onto the support in an amount that is less than about 20 wt % of the Group 8 metal, based on the total weight of the catalyst compound and support.

    [0172] In general, acetylenic compounds useful in this invention may contain a chelating moiety of the formula (VIII)

    ##STR00031##

    [0173] wherein,

    [0174] D is a leaving group;

    [0175] R.sup.16 to R.sup.17 are as defined below;

    [0176] R.sup.16 is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkyl sulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R.sup.16 is aryl, polyaryl, or heteroaryl, R.sup.16 may be substituted with any combination of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 and can be linked with any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 to form one or more cyclic aromatic or non-aromatic groups.

    [0177] R.sup.17 is selected from annulenes, having the general formula C.sub.nH.sub.n (when n is an even number) or C.sub.nH.sub.n+1 (when n is an odd number). Well-know representative compounds of annulenes, but not limited, are cyclobutadiene, benzene, and cyclooctatetraene. Annulenes can be aromatic or anti-aromatic. Every H-atom from the annulene fragment can be substituted by halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkyl sulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R.sup.17 is aryl, polyaryl, or heteroaryl, R.sup.17 may be substituted with any combination of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and can be linked with any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 to form one or more cyclic aromatic or non-aromatic groups.

    [0178] Examples of suitable leaving groups include, but are not limited to, hydroxyl, halide, ester, perhalogenated phenyl, acetate, benzoate, C.sub.2-C.sub.6 acyl, C.sub.2-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkyl, phenoxy, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylsulfanyl, aryl, or C.sub.1-C.sub.6 alkylsulfonyl. In even more preferred embodiments, D is selected from hydroxyl, halide, CF.sub.3CO.sub.2, CH.sub.3CO.sub.2, CFH.sub.2CO.sub.2, (CH.sub.3).sub.3CO.sub.3(CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In particular embodiments, D is advantageously hydroxyl (OH).

    [0179] Preferred organic acetylenic compounds are of the formula (IX),

    ##STR00032##

    [0180] Wherein

    [0181] m* is an integer from 1 to 5;

    [0182] R* is selected from R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6, or combinations thereof, as defined above.

    [0183] D and R.sup.16 are as defined above.

    [0184] Preferred organic acetylenic compounds include:

    ##STR00033##

    [0185] Synthesis of Metathesis Catalyst Compounds

    [0186] The catalyst compounds described in this invention may be synthesized by any methods known to those skilled in the art.

    [0187] Representative methods of synthesizing the Group 8 catalyst compound of the type described herein include, for example, treating a solution of the acetylenic compound in a suitable solvent, such as dioxane, with a reactant complex of a Group 8 metal, such as dichlorobis-(triphenylphosphine)ruthenium(II) and hydrogen chloride (in dioxane). The reaction mixture may be heated, for a time period appropriate to yield the desired modified indenylidene catalyst compound. Typically, removal of the volatiles and washed with hexane affords the Group 8 modified indenylidene 1.sup.st generation compound (Scheme 4) in high yields (>80%).

    [0188] A phosphine ligand, such as tricyclohexylphosphine, cyclohexyl-phosphabicyclononane, a phosphinite or a phosphinite may be added thereafter, if desired. The reaction conditions typically include mixing the Group 8 reactant compound and the preferred phosphine ligand in a suitable solvent, e.g. dichloromethane, for a time sufficient to effectuate the phosphine ligand exchange, at a suitable temperature typically ambient, yield (>90%).

    [0189] A N-Heterocyclic carbenes (NHC), such as 1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene or a CAAC may be added 1.sup.st generation compound (Scheme 4), if desired. The reaction conditions typically include mixing the Group 8 reactant 1.sup.st generation compound (Scheme 4) and the preferred NHC, CAAC ligand in a suitable solvent, e.g. toluene, for a time sufficient to effectuate the phosphine ligand exchange, at a suitable temperature typically between ambient and 80 C. Addition of isopropanol followed by filtration and washing, the desired 2.sup.nd generation compound (Scheme 4) is obtained in high yield (>85%).

    [0190] A pyridine ligand, such as pyridine, 3-Br pyridine may be added 2.sup.nd generation compound (Scheme 4), if desired. The reaction conditions typically include mixing the Group 8 reactant 2.sup.nd generation compound (Scheme 4) and the preferred pyridine ligand in as solvent, for a time sufficient to effectuate the phosphine ligand exchange, at a suitable temperature typically between ambient and 80 C. Filtration and washing gives the desired 3.sup.rd generation compound (Scheme 4) in high yield (>85%).

    ##STR00034##

    [0191] Scheme 4: different generations of non-chelating modified indenylidene catalysts.

    [0192] Treating a solution of the ditopic (or multitopic) ligand, e.g. O,N-bidentate ligands, in a suitable solvent, such as THF, with a 1.sup.st or 2.sup.nd or 3.sup.rd generation non-chelating modified indenylidene complex (see scheme 4), e.g. (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene in a 1:1 ratio and adding a required amount of silver (e.g. AgO.sub.2) for a time sufficient to effectuate the ligand exchange, at a suitable temperature typically between ambient and 80 C. to yield the desired modified indenylidene catalyst compound. The reaction temperature was then lowered to room temperature, the white precipitate of PCy.sub.3AgCl (byproduct) and excess of Ag.sub.2O was removed by filtration and the filtrate was concentrated under reduced pressure. The isolated solid residue provides the desired product (type I) in high yield (>85%).

    [0193] Treating a solution of the ditopic (or multitopic) ligand, e.g. O,N-bidentate ligands, in a suitable solvent, such as THF, with a 1.sup.st or 2.sup.nd or 3.sup.rd generation non-chelating modified indenylidene complex (see scheme 4), e.g. (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene in a 2:1 ratio and adding an equivalent amount of silver (e.g. AgO.sub.2) for a time sufficient to effectuate the ligand exchange, at a suitable temperature typically between ambient and 80 C. to yield the desired modified indenylidene catalyst compound. The reaction temperature was then lowered to room temperature, the white precipitate of PCy.sub.3AgCl (byproduct) and excess of Ag.sub.2O was removed by filtration and the filtrate was concentrated under reduced pressure. The isolated solid residue provides the desired product (type II) in high yield (>85%).

    [0194] Treating a solution of the ditopic (or multitopic) ligand, e.g. O,N-bidentate ligands, in a suitable solvent, such as THF, with a catalyst of type I in a 1:1 ratio and adding a required amount of silver (e.g. AgO.sub.2) for a time sufficient to effectuate the ligand exchange, at a suitable temperature typically between ambient and 80 C. to yield the desired modified indenylidene catalyst compound. The reaction temperature was then lowered to room temperature, the white precipitate of PCy.sub.3AgCl (byproduct) and excess of Ag.sub.2O was removed by filtration and the filtrate was concentrated under reduced pressure. The isolated solid residue provides the desired product (type II) in high yield.

    [0195] The exchange of the ditopic (or multitopic) ligands can also be performed by generating first the salt of the ligand (Sodium, Potassium, Magnesium, Thallium salts, . . . ) as is well-know by persons skilled in the art.

    [0196] Examples, but not limited, of ditopic or multitopic ligands are described in WO2005035121, European patent 1 468 004, EP 08 290 747.

    [0197] While the present invention describes a variety of transition metal complexes useful in catalyzing metathesis reactions, it should be noted that such complexes may be formed in situ. Accordingly, additional ligands may be added to a reaction solution as separate compounds, or may be complexed to the metal center to form a metal-ligand complex prior to introduction to the reaction.

    [0198] Synthetic protocols for representative 1,1-substituted prop-2-yn-1-ol ligands, ditopic, multitopic ligands and the corresponding ruthenium alkylidene complexes are as follows. Other substituted prop-2-yn-1-ol, ditopic, multitopic ligands and their respective metal complexes may be derived analogously.

    Example 1: 2-[(4-bromo-2,6-dimethylphenylimino)methyl]-4-nitrophenoxy (PCy.SUB.3.)(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (1F)

    Synthesis of (PPh.SUB.3.).SUB.2.Cl.SUB.2.Ru(3-2-methylphenyl-5-methylinden-1-ylidene) (1D)

    [0199] ##STR00035##

    Step 1: Bis(2-methylphenyl)methanone (1A)

    [0200] To a solution of 2-bromotoluene (2 eq., 2.6 ml, 21.79 mmol,) in 26 ml diethyl ether at 90 C., t-BuLi (1.9 M in pentane) (3 eq., 32.7 mmol, 17.2 ml.) was added drop wise. The solution was stirred for 30 min. at room temperature, followed by drop wise addition of N,N-dimethylcarbamoyl chloride (1 eq., 1 ml, 10.9 mmol), the reaction mixture was stirred for another 3 hours. The crude reaction mixture was quenched using 35 ml 1N HCl and diluted with diethyl ether. The organic phase was washed with water and the aqueous phase was extracted twice with diethyl ether, thereafter the ether fractions were combined and dried with anhydrous MgSO.sub.4. Removal of MgSO.sub.4 by filtration followed by purification using flash column chromatography (silica gel, hexane as solvent) and finally evaporation of the solvent and a white solid was obtained 0.93 g (40.6%).

    [0201] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 7.38 (td, 2H), 7.29 (td, 4H), 7.20 (td, 2H), 2.44 (s, 6H).

    [0202] .sup.13C NMR (75 MHz, CDCl.sub.3): 200.79, 139.01, 138.17, 131.43, 131.07, 130.31, 125.42, 20.67.

    Step 2: 1,1-bis-methylphenyl-3-(trimethylsilyl)prop-2-yn-1-ol (1B)

    [0203] n-BuLi (2.5 M in hexanes) (1.5 eq., 5.7 ml, 14.28 mmol,) was added drop wise to stirred solution of trimethylsilylacetylene (1.5 eq., 2 ml, 14.28 mmol) in anhydrous THF (17 ml) at 90 C. under an argon atmosphere. After addition, the resulting solution was stirred for another 5 min in a cold bath followed by stirring for 30 minutes at room temperature. Thereafter, bis(2-methylphenyl)methanone (9.52 mmol, 2 g) in 17 ml dry THF was added slowly to the solution at 90 C. and the resulting mixture was allowed to heat up and refluxed for 30 min. The crude reaction mixture was quenched using 15 ml 1N HCl and diluted with diethyl ether. The organic phase was washed with water and the aqueous phase were combined and extracted twice with ether, thereafter the ether fractions were combined and dried with anhydrous MgSO.sub.4. After removal of MgSO.sub.4 by filtration, and evaporation of the solvent a yellow liquid was obtained in quantitative yield. The obtained product was used without further purification.

    [0204] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 7.95 (dd, 2H), 7.27 (dd, 4H), 7.15 (dd, 2H) 2.75 (s, 1H) 2.14 (s, 6H), 0.27 (d, 9H).

    [0205] .sup.13C NMR (75 MHz, CDCl.sub.3): 141.01, 136.76, 132.37, 128.13, 127.45, 125.58, 107.10, 92.44, 75.01, 21.40, 0.00.

    Step 3: 1,1-bis-2-methylphenyl-prop-2-yn-1-ol (1C)

    [0206] A solution of 1,1-bis-methylphenyl-3-(trimethylsilyl)prop-2-yn-1-ol was obtained from previous step and K.sub.2CO.sub.3 (1 eq, 1.3 g 9.52 mmol) in dry methanol (10 ml) was stirred at room temperature for 3 h. The crude reaction mixture was quenched using 20 ml 1N HCl and diluted with diethyl ether. The organic phase was washed with water and the aqueous phase was extracted twice with diethyl ether, thereafter the ether fractions were combined and dried on anhydrous MgSO.sub.4. Removal of MgSO.sub.4 by filtration followed by purification using flash column chromatography (silica gel, Hexane/EtOAc=30/1) and finally evaporation of the solvent a yellowish solid (2.06 g, 92% yield for step 2+3) was obtained.

    [0207] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 7.95 (m, 2H), 7.23 (m, 4H), 7.09 (m, 2H) 2.89 (s, 1H) 2.67 (s, 1H), 2.02 (s, 6H).

    [0208] .sup.13C NMR (75 MHz, CDCl.sub.3): 140.60, 136.33, 132.30, 128.19, 127.24, 125.58, 85.52, 76.80, 74.75, 21.16.

    [0209] ESI[M-OH]: 219.1, calculated: 219.1.

    Step 4: (PPh.SUB.3.)Cl.SUB.2.Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene) (1D)

    [0210] (PPh.sub.3).sub.3RuCl.sub.2 (1 eq., 0.575 g, 0.6 mmol) and 1,1-bis-2-methylphenyl-prop-2-yn-1-ol (compound C, 1.5 eq., 0.213 g, 0.9 mmol) were added in 4 ml HCl/dioxane solution (0.15 mol/1). The solution was heated to 90 C. for 3 hour, after which the solvent was removed under vacuum. Hexane (20 ml) was added to the flask and the solid was ultrasonically removed from the wall. The resulting suspension was filtered and washed two times using hexane (5 ml). The remaining solvent was evaporated affording a red-brown powder; 0.52 g (Yield: 95%). The product was characterized by NMR spectra .sup.1H and .sup.31P.

    [0211] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 7.56 (dd, 11H), 7.37 (t, 6H), 7.21-7.31 (m, 13H), 7.09 (tetra, 3H), 6.95 (t, 3H), 6.47 (t, 1H), 6.14 (s, 1H), 2.20 (s, 3H), 1.66 (s, 3H).

    [0212] .sup.31P NMR (121.49 MHz, CDCl.sub.3): 29.33.

    Step 5: Synthesis of (PCy.SUB.3.).SUB.2.Cl.SUB.2.Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (1E)

    [0213] ##STR00036##

    [0214] A 25 ml vial was charged with (PPh.sub.3).sub.2Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene) (1 eq., 0.4574 g, 0.5 mmol), tricyclohexylphosphine (3 eq., 0.42 g, 1.5 mmol) and dichloromethane (10 ml). After completion of the reaction (1 h) the resulting slurry was dried under vacuum and 20 ml isopropanol was added. Filtration afforded a red-brown powder, which after washing with 5 ml isopropanol (2) and drying under vacuum afforded 0.44 g of catalyst (Yield: 93%). The product was characterized by NMR spectra .sup.1H and .sup.31P.

    [0215] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 8.54 (d, 1H), 7.24-7.29 (m, 1H), 7.10-7.17 (m, 4H), 7.07 (s, 1H), 7.02 (d, 1H), 2.61 (d, 6H), 2.22 (s, 3H), 1.18-1.96 (m, 63H).

    [0216] .sup.31P NMR (121.49 MHz, CDCl.sub.3): 31.75, 31.56.

    [0217] Characteristic values of .sup.1H and .sup.31P: HC8: 8.54 ppm (d, 1H) and P: 31.75 and 31.56 ppm.

    Step 6: Synthesis of 2-[(4-bromo-2,6-dimethylphenylimino)methyl]-4-nitrophenoxy (PCy.SUB.3.)(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (1F)

    [0218] ##STR00037##

    [0219] (PCy.sub.3).sub.2Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.53 mmol) and 2-[(4-bromo-2,6-dimethylphenylimino)methyl]-4-nitrophenol (0.53 mmol) (synthesized according the literature), silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0220] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 1F.

    [0221] Characteristic values of .sup.1H and .sup.31P: HC8: 6.75 ppm (d, 1H) and P: 39.65 ppm.

    [0222] The isolated solid residue was recrystallized from pentane to provide the catalyst. Yield after recrystallization: 75%.

    Example 2: Synthesis of (S-IMes)(2-[(2-methylphenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (2B)

    Step 1: Synthesis of (S-IMes)(PCy.SUB.3.)Cl.SUB.2.Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene) (2A)

    [0223] ##STR00038##

    S-IMes=saturated 1,3-bis(mesityl)-imidazolidine-2-ylidene (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)

    [0224] A 10 mL vial was charged with (PCy.sub.3).sub.2Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene) (1 eq., 0.3804 g, 0.4 mmol) and 5-IMes (1.1 eq., 0.134 g, 0.44 mmol). Dry toluene (3 ml) was added under inert atmosphere. The mixture was vigorously stirred at 50 C. for 30 minutes and dried under vacuum followed by addition of 10 ml isopropanol. After filtration and washing (two times 5 ml isopropanol), an orange powder was obtained; 0.33 g (Yield: 84%). The product was characterized by NMR spectra .sup.1H, .sup.13C, and .sup.31P.

    [0225] .sup.1H NMR (300 MHz, CDCl.sub.3, TMS): 8.47 (d, 1H), 7.44 (dd, 1H), 7.20-7.28 (m, 2H), 7.04-7.11 (m, 3H), 6.99 (d, 1H), 6.93 (s, 1H), 6.88 (d, 1H), 6.81 (s, 1H), 6.05 (s, 1H), 3.70-4.07 (m, 4H), 2.74 (s, 3H), 2.68 (s, 3H), 2.38 (s, 3H), 2.33 (s, 3H), 2.14 (s, 3H), 2.02 (s, 3H), 1.87 (s, 3H), 0.86-1.83 (m, 36H).

    [0226] .sup.13C NMR (75 MHz, CDCl.sub.3): 294.06, 293.96, 217.16, 216.19, 143.91, 140.11, 139.79, 139.52, 139.39, 138.77, 138.29, 136.94, 136.85, 136.27, 135.69, 134.04, 130.70, 130.01, 129.88, 129.57, 128.94, 128.58, 128.14, 127.25, 127.13, 126.27, 125.30, 125.05, 52.68, 52.64, 52.29, 52.26, 33.09, 32.87, 29.47, 29.24, 27.70, 27.57, 26.20, 21.18, 20.91, 20.32, 20.15, 19.36, 18.97, 18.92, 18.44.

    [0227] .sup.31P NMR (121.49 MHz, CDCl.sub.3): 26.75.

    Step 2: Synthesis of (S-IMes)(2-[(2-methylphenylimino)methyl]-4-nitrophenoxy)(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (2B)

    [0228] ##STR00039##

    [0229] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene)(0.51 mmol) and 2-[(2-methylphenylimino)methyl]-4-nitrophenol (0.51 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0230] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 2B.

    [0231] Characteristic values of .sup.1H: HC8: 8.39 ppm (d, 1H). (no .sup.31P NMR peak present in the complex)

    [0232] The isolated solid residue provided the catalyst in 85% yield.

    Example 3: (S-IMes)(2-[(2-chlorophenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (3A)

    [0233] ##STR00040##

    [0234] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene) (0.51 mmol) and 2-[(2-chlorophenylimino)methyl]-4-nitrophenol (0.51 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0235] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 3A.

    [0236] Characteristic values of .sup.1H: HC8: 8.33 ppm (d, 1H). (no .sup.31P NMR peak present in the complex)

    [0237] The isolated solid residue provided the catalyst in 87% yield.

    Example 4: Synthesis of (S-IMes)(2-[(4-bromo-2,6-dimethylphenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (4A)

    [0238] ##STR00041##

    [0239] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[(4-bromo-2,6-dimethylphenylimino)methyl]-4-nitrophenol (0.53 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0240] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 4A.

    [0241] Characteristic values of .sup.1H: HC8: 8.45 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0242] The isolated solid residue provided the catalyst in 89% yield.

    Example 5: Synthesis of (S-IMes)(2-[(2,6-dimethylphenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (5A)

    [0243] ##STR00042##

    [0244] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[(2,6-dimethylphenylimino)methyl]-4-nitrophenol (0.53 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0245] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex 5A.

    [0246] Characteristic values of .sup.1H: HC8: 8.87 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0247] The isolated solid residue provided the catalyst in 91% yield.

    Example 6: Synthesis of (S-IMes)(2-[(2,6-dimethylphenylimino)methyl]phenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (6A)

    [0248] ##STR00043##

    [0249] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[(2,6-dimethylphenylimino)methyl]-phenol (0.53 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0250] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex X6A.

    [0251] Characteristic values of .sup.1H: HC8: 9.10 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0252] The isolated solid residue provided the catalyst in 91% yield.

    Example 7: Synthesis of (S-IMes)(2-[(2,6-dimethylphenylimino)methyl]-4-methoxyphenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (7A)

    [0253] ##STR00044##

    [0254] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[(2,6-dimethylphenylimino)methyl]-4-methoxyphenol (0.53 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0255] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex 7A.

    [0256] Characteristic values of .sup.1H: HC8: 9.15 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0257] The isolated solid residue provided the catalyst in 87% yield.

    Example 8: Synthesis of (S-IMes)(2-[(pentafluorophenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (8A)

    [0258] ##STR00045##

    [0259] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[pentafluorophenylimino)methyl]-4-nitrophenol (0.53 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0260] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex 8A.

    [0261] Characteristic values of .sup.1H: HC8: 8.25 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0262] The isolated solid residue provided the catalyst in 82% yield.

    Example 9: Synthesis of (S-IMes)(2-[(3s,5s,7s)-adamantan-1-ylimino methyl]-4-nitrophenoxy)(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (9A)

    [0263] ##STR00046##

    [0264] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.51 mmol) and 2-[(3s,5s,7s)-adamantan-1-yliminomethyl]-4-nitrophenol (0.51 mmol) and silver(I) oxide (0.31 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0265] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 9A.

    [0266] Characteristic values of .sup.1H: HC8: 8.39 ppm (d, 1H). (no .sup.31P NMR peak present in the complex)

    [0267] The isolated solid residue provided the catalyst in 84% yield.

    Example 10: Synthesis of (2-[(2-methylphenylimino)methyl]-4-nitrophenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (10D)

    Synthesis of (PPh.SUB.3.).SUB.2.Cl.SUB.2.Ru(3-i-propyl-inden-1-ylidene) (10B)

    [0268] ##STR00047##

    Step 1: 1-i-propyl-1-phenyl-prop-2-yn-1-ol (10A)

    [0269] Ethynylmagnesium bromide (1.2 eq, 12.7 mmol, 25.4 ml) (0.5M in THF) was added to (i-propyl)(phenyl)methanone (1 eq., 10.6 mmol, 1.57 g) in dry THF (7 ml). The resulting solution was allowed to heat up under reflux overnight. The crude mixture was quenched by addition of 1N HCl (15 ml) and diluted with diethyl ether. The organic layer was separated; the aqueous layer was extracted twice with diethyl ether. The organic layers were combined dried on anhydrous MgSO.sub.4, filtered, and concentrated under vacuum. The product obtained after column chromatography (Hexane: EtOAc 20:1) is a yellow liquid 1.75 g yield 95%.

    [0270] .sup.1H NMR (300 MHz, CDCl.sub.3): 7.61 (dt, 2H), 7.22-7.36 (m, 3H), 2.66 (s, 1H), 2.50 (s, 1H), 2.09 (sept, 1H), 1.06 (d, 3H), 0.81 (d, 3H).

    [0271] .sup.13C NMR (75 MHz, CDCl.sub.3): 143.42, 127.95, 127.74, 126.14, 85.03, 77.07, 74.99, 40.16, 17.90, 17.38.

    Step 2: (PPh.SUB.3.).SUB.2.Cl.SUB.2.Ru(3-i-propyl-inden-1-ylidene) (10B)

    [0272] (PPh.sub.3).sub.3RuCl.sub.2 (1 eq., 0.575 g, 0.6 mmol) and 1-(i-propyl)-1-phenylprop-2-yn-1-ol (compound 18A, 1.5 eq., 0.144 g, 0.9 mmol) were added in 4 ml HCl/dioxane solution (0.15 mol/1). The solution was heated to 90 C. for 3 hour, after which the solvent was removed under vacuum. Hexane (20 ml) was added to the flask and the solid was ultrasonically removed from the wall. The resulting suspension was filtered and washed two times using hexane (5 ml). The remaining solvent was evaporated affording a red-brown powder; 0.48 g (Yield: 93%). The product was characterized by NMR spectra .sup.31P.

    [0273] .sup.31P NMR (121.49 MHz, CDCl.sub.3): 29.55.

    Step 3: Synthesis of (PCy.SUB.3.).SUB.2.Cl.SUB.2.Ru(3-i-isopropyl-inden-1-ylidene) (10C)

    [0274] ##STR00048##

    [0275] A 25 ml vial was charged with (PPh.sub.3).sub.2Cl.sub.2Ru(3-i-propyl-inden-1-ylidene) (1 eq., 0.4260 g, 0.5 mmol), tricyclohexylphosphine (3 eq., 0.42 g, 1.5 mmol) and dichloromethane (10 ml). After completion of the reaction (1 h) the resulting slurry was dried under vacuum and 20 ml isopropanol was added. Filtration afforded a red brown powder, which after washing with 5 ml isopropanol (2) and drying under vacuum afforded 0.40 g of catalyst (Yield: 90%). The product was characterized by NMR spectra .sup.1H and .sup.31P.

    [0276] Characteristic values of .sup.1H and .sup.31P: HC8: 8.57 ppm (d, 1H) and P: 31.44 ppm.

    Step 4: Synthesis of (2-[(2-methylphenylimino)methyl]-4-nitrophenoxy)(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (10D)

    [0277] ##STR00049##

    [0278] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-isopropyl-inden-1-ylidene) (0.50 g, 0.55 mmol) and 2-[(2-methylphenylimino)methyl]-4-nitrophenol (0.14 g, 0.55 mmol), and silver(I) oxide (0.33 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0279] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex 10D.

    [0280] Characteristic values of .sup.1H: HC8: 8.29 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0281] The isolated solid residue provided the catalyst in 84% yield.

    Example 11: Synthesis of (PCy.SUB.3.)(2-[(1-imidazole-3-propylimino)methyl]-phenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (11B)

    Step 1: Synthesis of (1-imidazole-3-propylimino)methyl-phenol (11A)

    [0282] Salicylaldehyde (37.54 mmol, 4.00 mL), 1-(3-aminopropyl)imidazole (37.54 mmol, 4.50 mL) and 15 ml ethyl alcohol were added to a 100 ml flask and refluxed for 4 hours. The resulting yellow solution was cooled overnight, filtered and washed with cold ethanol (31 mL). Bright yellow crystals were isolated in 90% yield.

    [0283] .sup.1H NMR (300 MHz, CDCl.sub.3) 13.09 (s, 1H), 8.25 (s, 1H), 7.39 35 (s, 1H), 7.26 (t, J=7.8 Hz, 1H), 7.18 (d, J=8.2 Hz, 1H), 7.01 (s, 1H), 6.93-6.79 (m, 3H), 4.00 (t, J=6.9 Hz, 2H), 3.48 (t, J=6.5 Hz, 2H), 2.12 (p, J=6.7 Hz, 2H). .sup.13C NMR (75 MHz, CDCl.sub.3) 166.10, 160.90, 137.11, 132.57, 131.42, 129.79, 118.99, 116.98, 40 77.48, 76.64, 55.86, 44.30, 31.78 MS (EI, 70 eV, rel. intensity): 229 (100, M.sup.+).

    Step 2: Synthesis of Synthesis of (PCy.SUB.3.)(2-[(1-imidazole-3-propylimino)methyl]-phenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (11B)

    [0284] ##STR00050##

    [0285] (PCy.sub.3).sub.2Cl.sub.2Ru(3-2-methylphenyl-5-methyl-inden-1-ylidene (0.53 mmol) and (1-imidazole-3-propylimino)methyl-phenol (0.53 mmol), silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (50 C.) and stirred for a period of 4 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure.

    [0286] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 11B.

    [0287] Characteristic values of .sup.1H and .sup.31P: HC8: 7.25 ppm (d, 1H) and P: 36.95 ppm.

    [0288] The isolated solid residue provided the catalyst in 75% yield.

    Example 12: Synthesis of (S-IMes)(2-[(2-methylphenylimino)methyl]phenoxy).SUB.2.(3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II) (12)

    Route A: Starting from (Simes)(PCy.SUB.3.)Cl.SUB.2.Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene) (2A)

    [0289] ##STR00051##

    [0290] (Simes)(PCy.sub.3)Cl.sub.2Ru(3-2-methylphenyl-5-methylphenyl-inden-1-ylidene) (0.51 mmol) and 2-[(2-methylphenylimino)methyl]phenol (1.1 mmol) and silver(I) oxide (0.65 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 5 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure. Addition of 2 mL CH.sub.2Cl.sub.2 and an excess of cold pentane precipitate the catalyst as a deep red powder, Yield: 85%.

    [0291] The reaction mixture was investigated on .sup.1H and .sup.31P NMR, which revealed quantitative transformation to complex 12.

    [0292] Characteristic values of .sup.1H: HC8: 8.11 ppm (d, 1H). (no .sup.31P NMR peak present in the complex)

    [0293] The reaction progress has been monitored using H-NMR, in FIG. 1 the reaction progress after 1 h is displayed. It is clear that this is still a mixture of the starting Ru-precursor, the ditopic O,N-ligand, the mono O,N-ruthenium complex and the bis O,N-ruthenium complex. FIG. 2 is Reaction progress after 5 h confirming completion of the reaction.

    Route B: starting from (SIMes)(2-[(2-methylphenylimino)methyl]phenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl

    [0294] ##STR00052##

    [0295] (SIMes)(2-[(2-methylphenylimino)methyl]phenoxy) (3-2-methylphenyl-5-methyl-inden-1-ylidene)Ru(II)Cl (0.51 mmol) and 2-[(2-methylphenylimino)methyl]phenol (0.52 mmol) and silver(I) oxide (0.32 mmol) were added to a Schlenk flask under argon. Dry THF (20 mL) was transferred to the Schlenk flask and then heated (40 C.) and stirred for a period of 5 h followed by cooling to room temperature. The white precipitate of PCy.sub.3AgCl (byproduct) and excess of AgO.sub.2 was removed by filtration. The filtrate was collected in a Schlenk flask and the solvent was removed by evaporation under reduced pressure. Addition of 2 mL CH.sub.2Cl.sub.2 and an excess of cold pentane precipitate the catalyst as a deep red powder, Yield: 85%.

    [0296] The reaction mixture was investigated on .sup.1H and .sup.31P-NMR, which revealed quantitative transformation to complex 12.

    [0297] Characteristic values of .sup.1H: HC8: 8.11 ppm (d, 1H). (no .sup.31P-NMR peak present in the complex)

    [0298] Performance of the Catalysts of Present Invention

    Example 13: Comparison of Commercial Available Catalyst (N) with Catalyst of this Invention 5A, 6A and 7A for RCM of DEDAM Using Activation .SUP.a

    [0299] FIG. 3 is comparison between commercial catalysts N and 5A, 6A and 7A for the ring-closing metathesis of diethyldiallylmalonate (DEDAM) using activation (.sup.a using catalyst N and chemically activated 5A, 6A and 7A at 0.5 mol %, 20 eq of PhSiCl.sub.3, substrate loading: 0.41 mmol DEDAM, temperature: 20 C., solvent: 0.60 mL CDCl.sub.3, conversion determined by .sup.1H NMR).

    [0300] Upon chemical activation, complexes 6A and 7A significantly outperform the commercial complex N at ambient temperature.

    Example 14: Effect of Catalyst Loading, Comparison of Commercial Available Catalyst (N) with Newly Developed Catalyst 5A, 6A and 7A for RCM of DEDAM after Activation

    [0301] FIG. 4 is comparison between catalysts F and 5A-7A at a 0.1 mol % loading for the RCM of DEDAM (.sup.a using catalyst F and chemically activated 5A-7A at 0.1 mol %, 10 eq of PhSiCl.sub.3, substrate loading: 0.41 mmol DEDAM, temperature: 20 C., solvent: 0.60 mL CDCl.sub.3, conversion determined by .sup.1H NMR).

    [0302] At lower catalyst loadings, catalyst lifetime becomes increasingly important. All of the Schiff base-containing catalysts described herein, upon activation by PhSiCl.sub.3, yield quantitative RCM of DEDAM at a catalyst loading of 0.1 mol % in CDCl.sub.3, at room temperature with the exception of 5A which requires 60 C. In all cases, the performance of the salicylaldimine systems 5A-7A is superior to that of the commercial available complex F.

    Example 15: Comparison of Commercial Available Catalysts (N) with Newly Developed Catalyst for RCM of DEDAM in Protic Solvent MeOH at 50 C.

    [0303]

    TABLE-US-00001 TABLE 1 Comparison of TON (Turn Over Number) of reported catalysts and catalyst of this invention Catalyst TON.sup.a Ref [00053]embedded image 8 Grubbs R. et al. Tetrahedron Letters 2005, 46, 2577-2580. [00054]embedded image 7 Blechert S. et al. Bioorganic & Medicinal Chemistry Letters 2002, 12, 1873-1876. [00055]embedded image 14 Blechert S. et al. Bioorganic & Medicinal Chemistry Letters 2002, 12, 1873-1876. [00056]embedded image 19 Raines R. et al. Advanced Synthesis & Catalysis 2007, 349, 395-404. [00057]embedded image 60 This invention [00058]embedded image 189 This invention [00059]embedded image 190 This invention .sup.aTON = Turn over Number; RCM of DEDAM using 0.5 mol % catalyst in MeOH-d.sub.4 at 50 C.

    Example 16: Comparison of Commercial Available Catalysts Catalyst of this Invention for RCM of DEDAM-2

    [0304] ##STR00060##

    [0305] It is well known that DEDAM-2 is a difficult substrate to ring-close since it bears a methyl group on each double bond which introduce severe sterical hindering for the catalyst.

    TABLE-US-00002 TABLE 2 Comparison of the catalysts for the reluctance substrate DEDAM-2 Loading T Catalyst (mol %) ( C.) TON.sup.a,b [00061]embedded image 0.5 100 44 4A [00062]embedded image 0.5 100 136 13* [00063]embedded image 0.5 100 110 14** [00064]embedded image 0.5 100 37 8A [00065]embedded image 5 100 7 [00066]embedded image 5 30 3.sup.c [00067]embedded image 2.5 60 38.sup.d Mod. H2 .sup.aConversion obtained by .sup.1H NMR. .sup.bPerformed in toluene. .sup.cPerformed in CD.sub.2Cl.sub.2, data from ref. (Organometallics 2006, 25, 5740). .sup.dPerformed in C.sub.6D.sub.6, data from ref. (Org. Lett. 2007, 9, 1589). *The catalyst has been prepared according to the description of 4A except that 2-[(2,6- diisopropylphenylimino)methyl]-4-nitrophenol was applied as ditopic ligand. **The catalyst has been prepared according to the description of 4A except that 2-[(2,4,6-trimethylphenylimino)methyl]-phenol was applied as ditopic ligand.

    [0306] The catalysts of this invention show 100% conversion at a 5 mol % loading. Decreasing the catalyst loading to 0.5 mol % leads to a TON of 136 for 13 and 110 for 14. These results outperform the previous highest TON of 38 for Mod. 112 (modified Hoveyda catalyst) and represent a 20-fold increase compared with the standard Grubbs 2.sup.nd generation catalyst. Therefore, 13 and 14 represent an excellent answer to a major challenge for the design of new more efficient catalysts.

    Example 17: Influence of the Amount of Activator on the Performance of Catalyst 6A of this Invention for RCM of DEDAM

    [0307] ##STR00068##

    [0308] Conditions: 0.5 mol % catalyst, variable eq of PhSiCl.sub.3, substrate loading: 0.41 mmol DEDAM, temperature: 20 C., solvent: 0.60 mL CDCl.sub.3, conversion determined by .sup.1H NMR.

    [0309] FIG. 5 is influence of activator amount (from top to bottom the amount decreases from 50 eq. to 0.5 eq PhSiCl.sub.3) on the catalytic performance for RCM of DEDAM.

    [0310] It is clear that no longer an excess of activator is required to activate the catalysts of this invention and clearly outperforms the systems described in EP 1 577 282; EP 1 757 613. Moreover, an excess of activator is not immediately decomposing the catalyst demonstrating the robustness of the systems.

    Example 18: Monitoring Ring Opening Metathesis Polymerization (ROMP) of Dicyclopentadiene (DCPD)

    [0311] The required amount was of catalyst was dissolved in a minimum amount of dichloromethane (CH.sub.2Cl.sub.2), and thereafter added to 80 g of DCPD which contains the required amount of activator (here PhSiCl.sub.3 was used). The mixture was stirred and the polymerization reaction was monitored as a function of time starting at 20 C. by a thermocouple which was placed inside the reaction mixture to collect the temperature data. catalyst/DCPD: 1/60000.

    [0312] The catalysts used are 4A, 8A, 9A and 12. For catalyst 4A and 8A the catalyst/activator=1/5 while for the 9A and 12 the catalyst/activator=1/0.5.

    [0313] FIG. 6 is ROMP of DCPD using catalyst 4A, 8A, 9A and 12 of this invention.

    [0314] A ruthenium catalysts Verpoort (WO 03/062253) and Telene (WO 2011/009721 A1) comprising one and two bidentate Schiff base ligand respectively have been used as a reference catalyst; see table 3.

    ##STR00069##

    [0315] It is clear that the catalysts of this invention outperform the catalysts described in WO 2011009721 and (WO 03/062253; Tetrahedron Lett., 2002, 43, 9101-9104; (b) J. Mol. Catal. A: Chern., 2006, 260, 221-226; (c) J. Organomet. Chem., 2006, 691, 5482-5486).

    [0316] Introducing extra groups, substituents on the indenylidene part of the catalysts result in more steric strain in the molecule which promotes the initiation of the catalyst once it is activated.

    TABLE-US-00003 TABLE 3 Comparison between existing catalyst (T and VP) and catalysts of this invention (4A, 8A, 9A and 12) for the ROMP of DCPD DCPD/ T.sub.max Tg.sub.1 Tg.sub.2 Catalyst Latency Cocatalyst Cl/Ru Ru ( C.) ( C.) ( C.) 9A fair PhSiCl.sub.3 0.5 50000 230 170 179 8A Good PhSiCl.sub.3 5 50000 223 168 175 4A Good PhSiCl.sub.3 5 50000 195 160 169 12 Good PhSiCl.sub.3 0.5 50000 223 171 179 T* Good PhSiCl.sub.3 2 30000 217 171 178 VP* Good PhSiCl.sub.3 45 30000 215 156 169 *for reference only

    [0317] All catalysts of this invention show an excellent latency towards DCPD (with 9A a fair latency), they are inactive at room temperature. All catalysts of this invention show an improved stability and are superior to other catalysts used as a reference (T and VP), see table 3.

    [0318] Upon chemical activation, the catalyst of type I-I, e.g. 12 and 9A, according to the present invention, demonstrate an increased initiation compared to the reference catalyst (T and VP) because it requires only less than 1 equivalent of PhSiCI.sub.3 to generate a highly active system. When the ROMP of DCPD is catalysed by the chemically activated VP complex (reference), under the same conditions (less than 1 equivalent of PhSiCI.sub.3) a low catalytic activity was observed.

    [0319] Moreover the ratio catalyst/monomer is increased with 66% compared to the reference catalysts (T and VP) which clearly stress out their superior performance of the catalysts of the present invention

    Example 19: Monitoring Ring Opening Metathesis Polymerization (ROMP) of Cyclo-Octadiene (COD)

    [0320] ##STR00070##

    [0321] After charging an NMR tube with the appropriate amount of catalyst dissolved in deuterated solvent (CDCl.sub.3), COD was added. The polymerization reaction was monitored as a function of time at 20 C. by integrating olefinic .sup.1H-signals of the formed polymer (5.38-4.44 ppm) and the consumed monomer (5.58 ppm).

    [0322] catalyst/COD: 1/3000, catalyst concentration: 0.452 mM.

    TABLE-US-00004 TABLE 4 ROMP of COD (3000 equiv). Catalyst/ T PhSiCl.sub.3 (equiv).sup.a [ C.] time [min] Conv. [%] cis [%].sup.b TOF (h.sup.1) G2.sup.[c]/0 RT 30 100 13 6 000 F/0 RT 45 100 60 .sup.600.sup.[d] N/0 RT 300 100 70 600 VP/20 RT 10 100 9 18 000 6A/5 RT 5 100 5 36 000 7A/5 RT 5 100 20 36 000 .sup.aConditions: Catalyst concentration: 0.453 mM, solvent: CDCl.sub.3, temperature: 20 C., conversion determined by .sup.1H NMR. .sup.bPercent olefin with cis configuration in the polymer backbone; ratio based on data from .sup.1H and .sup.13C NMR spectra (.sup.13C NMR spectroscopy: = 32.9 ppm allylic carbon trans; = 27.6 ppm allylic carbon cis). .sup.[c]see Nature 2007, 450, 243-251.]. .sup.[d]monomer/catalyst = 300.

    [0323] The catalysts of this invention are superior compared with other catalysts, the obtained TON is at least 2 times higher compared with catalyst VP and even 6 times higher or more compared with the other catalysts.

    Example 20: In-Situ Activation Using TiCl.SUB.4./iPrOH of Catalyst 4A for the ROMP of Dicyclopentadiene (DCPD)

    [0324] This example demonstrates the possibility of in-situ activation of the catalysts of this invention. Here 40 g of DCPD in which TiCl.sub.4 is present is mixed with 40 g of DCPD in which iPrOH and the catalyst are present. In the total DCPD mixture (80 g) a thermocouple is place to follow the temperature increase during the polymerization. From the plot it follows that all monomers are converted since a high temperature of 200 C. is reached. The ratio DCPD/catalyst/Lewis acid-alcohol=30000/1/10-10 and 30000/1/5-5.

    [0325] FIG. 7 is ROMP of DCPD using in-situ activation of catalyst 4A.

    [0326] This excellent results confirms that all kinds of combinations between Lewis acids and RYH molecules can be used for in-situ activation of the catalysts of this invention as described in the description

    Example 21: Removal of the Residual Ruthenium (11B) from the Reaction Mixture

    [0327] Subsequent to the RCM or cross-metathesis applications, in order to remove the residual ruthenium in final metathesis products, the reaction mixtures were passed through silica gel (3 g per 0.006 mmol of catalyst 11B) with different eluents (see Table 5). The silica gel can also be introduced directly into the reaction mixture. Complete decolorization was observed within 10 minutes of intense stirring. The ruthenium content of some selected metathesis products were determined by ICP-MS analysis. Using a basic filtration through silica gel, the ruthenium content of the products with an initial ruthenium content of 500 ppm were reduced to 1 ppm.

    TABLE-US-00005 TABLE 5 Residual ruthenium from reaction mixtures after column chromatography. Ru content Entry Product Eluent (ppm) 1 [00071]embedded image CH.sub.2Cl.sub.2 Toluene 1 1 2 Self-metathesis product of CH.sub.2Cl.sub.2 1 methy-10-undecenoate Toluene 3

    Example 22: Cross Metathesis of FAME (Fatty Acid Methyl Esters) Using Catalyst 4A

    [0328] 50 ml of a methyl ester mixture (consisting of 92.0% methyl oleate and 2.9% Methyl linoleate, percentages are based on a calibrated GC-Method) in the presence of 150 ppm of the catalyst (4A) is heated at 50 C. for 1 hour. After completion of the reaction 27% dimethyldiesters and 24% of 9-octadecene is obtained.