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WO2018191373A1 - Synthèse et caractérisation de catalyseurs de métathèse - Google Patents

Synthèse et caractérisation de catalyseurs de métathèse Download PDF

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WO2018191373A1
WO2018191373A1 PCT/US2018/027098 US2018027098W WO2018191373A1 WO 2018191373 A1 WO2018191373 A1 WO 2018191373A1 US 2018027098 W US2018027098 W US 2018027098W WO 2018191373 A1 WO2018191373 A1 WO 2018191373A1
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substituted
unsubstituted
propyl
phenyl
butyl
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Adam M JOHNS
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Materia Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts.
  • the invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.
  • ruthenium metathesis catalysts have enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), ring closing metathesis (RCM).
  • ROMP ring opening metathesis polymerization
  • CCM cross metathesis
  • RCM ring closing metathesis
  • N-Heterocyclic Carbene (NHC) ligands played an essential role in the development of ruthenium metathesis catalysts, giving rise to the Second Generation Grubbs ruthenium olefin metathesis catalysts, such as:
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula I):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 1 and L 2 are independently neutral electron donor ligands
  • n is 0 or 1 ; typically, n is 0;
  • m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0; R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X 1 and X 2 are independently chlorine, bromine, iodine or fluorine;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R 1 is hydrogen, and R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to
  • the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.
  • the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions.
  • the invention provides a method of synthesizing a Second Generation Grubbs catalyst, using an olefin metathesis catalyst of the invention.
  • Figure 1 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C801 TU.
  • Figure 2 depicts the reactivity in ring closing metathesis of diethyl diallylmalonate in the presence of olefin metathesis catalysts of the invention.
  • an olefin includes a single olefin as well as a combination or mixture of two or more olefins
  • reference to "a substituent” encompasses a single substituent as well as two or more substituents, and the like.
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to 30 carbon atoms, generally containing 1 to 24 carbon atoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl, f-butyl, octyl, decyl, and the like, as well as cycloalkyi groups such as cyclopentyl, cyclohexyl and the like.
  • lower alkyl intends an alkyl group of 1 to 6 carbon atoms
  • cycloalkyi intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms.
  • substituted alkyl refers to alkyl substituted with one or more substituent groups
  • 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 terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
  • alkylene refers to a divalent linear, branched, or cyclic alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, /so-propenyl, n-butenyl, /so-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
  • alkenyl groups herein contain 2 to 24 carbon atoms, typically “alkenyl” groups herein contain 2 to 12 carbon atoms.
  • lower alkenyl intends an "alkenyl” group of 2 to 6 carbon atoms
  • cycloalkenyl intends a cyclic “alkenyl” group, typically having 5 to 8 carbon atoms.
  • substituted alkenyl refers to "alkenyl” substituted with one or more substituent groups
  • heteroatom-containing alkenyl and heteroalkenyl refer to "alkenyl” in which at least one carbon atom is replaced with a heteroatom.
  • alkenyl and lower alkenyl include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing “alkenyl” and lower “alkenyl,” respectively.
  • alkenyl is used interchangeably with the term “olefin” herein.
  • alkenylene refers to a divalent linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n- propynyl, and the like. Generally, “alkynyl” groups herein contain 2 to 24 carbon atoms; typical “alkynyl” groups described herein contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an "alkynyl” group of 2 to 6 carbon atoms.
  • substituted alkynyl refers to “alkynyl” substituted with one or more substituent groups
  • 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 terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl” respectively.
  • alkoxy refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group can be represented as -O-alkyl where alkyl is as defined above.
  • a "lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
  • alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
  • alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
  • aryl 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).
  • Aryl contain 5 to 30 carbon atoms, generally “aryl” groups contain 5 to 20 carbon atoms; and typically, “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; for example 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2,6-di-/so-propylphenyl (i.e., DIPP or DiPP), 2-/so-propyl-phenyl (i.e., IPP, Ipp or ipp), 2-/so-propyl-6-methylphenyl (i.e., MIPP or Mipp or MiPP).
  • substituent groups for example 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2,6-di-/so-propylphenyl (i.e., DIPP or DiPP), 2-/so-propyl-phenyl (i.e., IPP, Ipp or ipp), 2-/so-propyl-6-methylphenyl (i.e.
  • aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above.
  • An “aryloxy” group can 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.
  • aryloxy groups include, without limitation, phenoxy, o-halo- phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
  • alkaryl refers to an aryl group with an alkyl substituent
  • aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Alkaryl and “aralkyl” groups contain 6 to 30 carbon atoms; generally, “alkaryl” and “aralkyl” groups contain 6 to 20 carbon atoms; and typically, “alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms.
  • Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1 ,4-diene, and the like.
  • 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.
  • alkaryloxy and aralkyloxy refer to substituents of the formula -OR wherein R is “alkaryl” or “aralkyl,” respectively, as defined herein.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)- aryl, or -(CO)-aralkyl
  • 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.
  • cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom-containing, and that can be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic, or polycyclic.
  • halo halogen
  • halide halogen
  • hydrocarbyl refers to univalent “hydrocarbyl” moieties containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, specifically containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
  • lower hydrocarbyl intends a “hydrocarbyl” group of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms
  • hydrocarbylene intends a divalent “hydrocarbyl” moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
  • lower hydrocarbylene intends a "hydrocarbylene” group of 1 to 6 carbon atoms.
  • 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.
  • 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.
  • 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.
  • heteroalkyl refers to an alkyl substituent that is heteroatom- containing
  • heterocyclic refers to a cyclic substituent that is heteroatom- containing
  • heteroaryl and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • heterocyclic group or compound may or may not be aromatic, and further that “heterocycles” can be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl.”
  • heteroalkyl groups include alkoxyaryl, alkylsulfanyl- substituted alkyl, N-alkylated amino alkyl, and the like.
  • heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1 ,2,4-triazolyl, tetrazolyl, etc.
  • 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.
  • substituents include, without limitation hydrocarbyl groups, as defined herein, as well as functional groups ("Fn"), such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy (-O-CO- alkyl) and C6-C24 arylcarbonyloxy (-O-CO-aryl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-aryl),
  • Fn
  • “functional ized” 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.
  • the term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.
  • 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.
  • the above-mentioned hydrocarbyl moieties can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula I):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 1 and L 2 are independently neutral electron donor ligands
  • n is 0 or 1 ; typically, n is 0; m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom- containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom- containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X 1 and X 2 are independently chlorine, bromine, iodine or fluorine;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (II):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically M is ruthenium;
  • L 1 is a carbene
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0; R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • X 3 and X 4 are independently 0 or S; typically, X 3 and X 4 are S; and
  • R x , R y , R w and R z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula III):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • n 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/t-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X 1 and X 2 are independently chlorine, bromine, iodine or fluorine; and R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • X and Y are independently C, CR 3a , N, 0, S, or P; only one of X or Y can be C or CR 3a ; typically, X and Y are both N;
  • Q 1 , Q 2 , R 3 , R 3a and R 4 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q 1 , Q 2 , R 3 , R 3a and R 4 are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or -(CO)-; typically Q 1 , Q 2 , R 3 , R 3a and R 4 are directly linked to X or Y; and
  • p is 0 when X is O or S, p is 1 when X is N, P or CR 3a , and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P or CR 3a , and q is 2 when X is C.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula IV):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • n 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • X and Y are independently C, CR 3a , N, 0, S, or P; only one of X or Y can be C or CR 3a ; typically, X and Y are both N;
  • Q 1 , Q 2 , R 3 , R 3a and R 4 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q 1 , Q 2 , R 3 , R 3a and R 4 are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or -(CO)-; typically Q 1 , Q 2 , R 3 , R 3a and R 4 are directly linked to X or Y; and
  • p is 0 when X is O or S, p is 1 when X is N, P or CR 3a , and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P or CR 3a , and q is 2 when X is C.
  • X 3 and X 4 are independently O or S;
  • R x , R y , R w and R z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein R x , R y , R w and R z are independently hydrogen, chlorine, fluorine, bromine, iodine, unsubstituted C1-C12 alkyl, unsubstituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, substituted C1-C12 alkyl, substituted C3-C10 cycloalkyl, substituted C5-C24 aryl, unsubstituted heteroalkyl, unsubstituted cycloheteroalkyl, unsubstituted heteroaryl, substituted heteroalkyl, substituted cycloheteroalkyl, substituted heteroaryl.
  • R x , R y , R w and R z are independently hydrogen, chlorine, fluorine, bromine, iodine, unsubstituted C1-C
  • the substitutents can be selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, and carbamate.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula V):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • n 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X 1 and X 2 are independently chlorine, bromine, iodine or fluorine;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted
  • X and Y are independently C, CR 3a , or N; only one of X or Y can be C or CR 3a ; typically, X and Y are both N;
  • R 3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
  • R 3 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 3 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • n 0, 1 or 2; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyi, substituted C1 -C10 alkyi, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryi or substituted C5-C24 aryi; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyi, substituted C1 -C10 alkyi, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryi or substituted C5-C24 aryi; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 is a 2-electron anionic donor bridging moiety linking R 3 and Ru;
  • X 2 is a bidentate anionic ligand selected from: nitrate (NO3 " ), C1-C20 alkylcarboxylate, C6-C24 arylcarboxylate, C2-C24 acyloxy, C1 -C20 alkylsulfonato, C5-C24 arylsulfonato, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1 -C20 alkylsulfinyl, or C5-C24 arylsulfinyl; generally X 2 is benzoate, pivalate, or nitrate; typically X 2 is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH 3 ) 3 C02, (CH 3 ) 2 CHC02, (CF 3 )2(CH 3 )C02, (CF 3 )(CH 3 )2C02, benzoate, naphthylate
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted in
  • R 3 is adamantane-2, 1 -diyl
  • R 4 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 4 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), or (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 araikyi, substituted C6
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VI):
  • M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;
  • L 2 is a neutral electron donor ligand
  • n is 0 or 1 ; typically, n is 0;
  • n 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X 1 and X 2 are independently chlorine, bromine, iodine or fluorine;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted in
  • R 3a is hydrogen, unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi;
  • R 3 is unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi; generally, R 3 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-
  • R 4 is unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi; generally, R 4 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), or (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyi, substituted C6-
  • X 3 and X 4 are independently 0 or S; typically, X 3 and X 4 are S; and
  • R x , R y , R w and R z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R x , R y , R w and R z are typically hydrogen, chlorine, florine, bromine, iodine, methyl, ethyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, cyclopropyl, phenyl; typically, R x and R z are independently chlorine and R y and R w are independently hydrogen.
  • R 1 is hydrogen;
  • R 2 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally, X 1 and X 2 are independently chlorine, bromine, iodine or fluorine; typically, X 1 and X 2 are chlorine;
  • R 3 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 3 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24
  • R 4 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 4 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24
  • R 1 is hydrogen
  • R 2 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • X 1 is a 2-electron anionic donor bridging moiety linking R 3 and Ru;
  • X 2 is a bidentate anionic ligand selected from: nitrate (NO3 " ), C1-C20 alkylcarboxylate, C6-C24 arylcarboxylate, C2-C24 acyloxy, C1 -C20 alkylsulfonato, C5-C24 arylsulfonato, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1 -C20 alkylsulfinyl, or C5-C24 arylsulfinyl; generally X 2 is benzoate, pivalate, or nitrate; typically X 2 is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH 3 ) 3 C02, (CH 3 ) 2 CHC02, (CF 3 )2(CH 3 )C02, (CF 3 )(CH 3 )2C02, benzoate, naphthylate
  • R 3 is adamantane-2, 1 -diyl
  • R 4 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 4 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24
  • R 1 is hydrogen; .e.,
  • R 1 and R 2 are linked together to form 3-phenylinden-1 -ylidene (i.e., );
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, benzyl or phenyl; or
  • R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, benzyl or phenyl; or
  • R c and R d are linked to form morpholine or piperidine;
  • R b and R c are linked to form 1 ,3-dimethylimidazole;
  • R 3 is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-isopropyl-6-methyl phenyl;
  • R 4 is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-isopropyl-6-methyl phenyl.
  • R 1 is hydrogen
  • R 2 is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl; or
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine; and R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/t-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R a and R b are linked to form morpholine or piperidine;
  • R c and R d are linked to form morpholine or piperidine;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R b and R c are linked to form 1 ,3-dimethylimidazole;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,
  • R a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;
  • R b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R a and R b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c and R d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;
  • R b and R c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;
  • R 1 and R 2 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R 2 is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R 1 and R 2 are linked together to form an optionally substituted
  • R 3 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 3 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1-C20 alkyl, substituted C1-C20 alkyl, unsubstituted C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl
  • R 4 is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R 4 is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1-C20 alkyl, substituted C1-C20 alkyl, unsubstituted C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralky
  • X 3 and X 4 are independently 0 or S; typically, X 3 and X 4 are S; and
  • R x , R y , R w and R z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R x , R y , R w and R z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R x , R y , R w and R z are hydrogen, chlorine, florine, bromine, iodine, methyl, ethyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, cyclopropyl, phenyl; R x and R z are independently chlorine and R y and R w
  • R 1 is hydrogen;
  • R 2 is phenyl, 2-iso- propoxy-phenyl, or 2-methyl-1 -propenyl; or R 1 and R 2 are linked together to form 3- phenylinden-1 -ylidene;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or
  • R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or
  • R c and R d are linked to form morpholine or piperidine;
  • R b and R c are linked to form 1 ,3-dimethylimidazole;
  • X 3 is S
  • X 4 is S
  • R 3 is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-/so-propyl-6-methyl phenyl;
  • R 4 is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-/so-propyl-6-methyl phenyl;
  • R x , R y , R w and R z are independently hydrogen, chlorine, fluorine, bromine or iodine.
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, fluorine, bromine or iodine;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R b and R c are linked to form 1 ,3-dimethylimidazole;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 and R 2 are linked to form 3- phenylindeny-1 -ylidene
  • R a and R b are linked to form morpholine or piperidine;
  • R c and R d are linked to form morpholine or piperidine;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 is hydrogen
  • R 2 is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl
  • R b and R c are linked to form 1 ,3-dimethylimidazole;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • R 1 is hydrogen
  • R 2 is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl
  • R a and R b are linked to form morpholine or piperidine;
  • R c and R d are linked to form morpholine or piperidine;
  • X 1 and X 2 are independently chlorine, bromine, fluorine or iodine;
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.
  • Table (2) Examples of olefin metathesis catalysts represented by the structure of Formula (VIII), wherein: R y is H, R w is H, R x is CI, R z is CI, X 3 is S and X 4 is S.
  • R 1 is hydrogen, R 2 is unsubstituted phenyl, substituted phenyl or alkenyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R c and R d are linked to form morpholine or piperidine; or R b and R c are linked to form 1 ,3-dimethylimidazole;
  • X 1 and X 2 are independently chlorine, bromine, iodine or fluorine; X 1 and X 2 are chlorine;
  • R 3 is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl- phenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-/so- propyl-6-methylphenyl or 2-methyl-phenyl.
  • R 1 is hydrogen
  • R 2 is unsubstituted phenyl, substituted phenyl or alkenyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R c and R d are linked to form morpholine or piperidine; or R b and R c are linked to form 1 ,3-dimethylimidazole;
  • X 1 is a 2-electron anionic donor bridging moiety linking R 3 and Ru;
  • X 2 is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH 3 ) 3 C02, (CH 3 ) 2 CHC02, (CF 3 )2(CH 3 )C02, (CF 3 )(CH 3 ) 2 C02, benzoate, naphthylate, tosylate, mesylate, or trifluoromethane-sulfonate or nitrate;
  • R 3 is adamantane-2, 1 -diyl
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-iso- propyl-6-methylphenyl or 2-methyl-phenyl.
  • R 1 is hydrogen
  • R 2 is phenyl, 2-/so-propoxy-phenyl or 2-methyl-1 -propenyl;
  • R 1 and R 2 are linked together to form 3-phenylinden-1 -ylidene
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl; or R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or R c and R d are linked to form morpholine or piperidine; or R b and R c are linked to form 1 ,3- dimethylimidazole;
  • X 1 and X 2 are chlorine
  • R 3 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl.
  • R 1 is hydrogen
  • R 2 is unsubstituted phenyl, substituted phenyl or alkenyl; or R 1 and R 2 are linked together to form an optionally substituted indenylidene;
  • R a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;
  • R b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R a and R b are linked to form morpholine or piperidine;
  • R c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;
  • R d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R c and R d are linked to form morpholine or piperidine; or R b and R c are linked to form 1 ,3-dimethylimidazole;
  • R 3 is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl- phenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl;
  • R 4 is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-/so- propyl-6-methylphenyl or 2-methyl-phenyl.
  • X 3 and X 4 are S;
  • R x and R z are independently chlorine
  • R y and R w are independently hydrogen.
  • the catalysts of the invention may be attached to a solid support.
  • the present invention also concerns processes for synthesizing the olefin metathesis catalysts of the invention.
  • the olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. For example, synthetic Scheme 1 , set forth below, illustrates how the compounds according to the invention can be synthesized.
  • R s , R l , and R u are each independently substituted C5-C24 aryl, unsubstituted C5-C24 aryl or substituted C1-C10 alkyl, unsubstituted C1-C10 alkyl; generally R s , R l , and R u are each independently unsubstituted C5-C24 aryl; typically R s , R l , and R u are each independently phenyl or cycohexyl.
  • the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (VI) starting with an olefin metathesis catalyst of Formula (V): Scheme 2
  • Formula (V) Formula (VI) wherein: M, R 1 , R 2 , R 3 , R 4 , R a , R b , R c , R d , X 1 , X 2 , Q, n, m, L 2 , X, Y, R x , Rv, R w , R z , X 3 and X 4 are as defined herein.
  • the thiourea olefin metathesis catalyst represented by the structure of Formula (V) can become a dithiolate derivative olefin metathesis catalyst represented by the structure of Formula (VI).
  • the invention concerns methods of using the olefin metathesis catalysts of the invention, in the synthesis of related olefin metathesis catalysts.
  • the ruthenium olefin metathesis catalysts bearing labile thiourea ligands of the invention are excellent precursors for various Second Generation Grubbs ruthenium olefin metathesis catalysts.
  • the Second Generation Grubbs ruthenium olefin metathesis catalysts synthesized during these procedures are obtained in very high yield and with very high purity, which presents an advantage compared to the existing synthetic procedures.
  • the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (B) starting with an olefin metathesis catalyst of Formula (V): Scheme 3
  • R 1 , R 2 , R 3 , R 4 , R a , R b , R c , R d , X 1 , X 2 , Q, n, m, L 2 , X and Y are as defined herein and "L" is selected from PR g OR h OR', PR k R e OR f , pyridine, trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(ortho-tolyl)phosphine (P-o- toly ), tri-tert-butylphosphine (P-fe/f-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), tri-/so-propylphosphine (P-i-Pr3), trioctylphosphine (POct3),
  • R g is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyi or unsubstituted C3-C8 cycloalkyi; generally, R g is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically R g is phenyl;
  • R h is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyi or unsubstituted C3-C8 cycloalkyi; generally R h is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R h is phenyl or methyl;
  • R' is unsubstituted C1 -C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R' is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R' is phenyl or methyl;
  • R k is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R k is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R k is phenyl;
  • R e is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R e is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically R e is phenyl;
  • R f is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R f is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R f is phenyl, methyl, /so-propyl or 4-methoxyphenyl.
  • the ligand exchange reactions are carried out under inert atmosphere (under nitrogen or argon).
  • the reactions generally are carried out at room temperature or at temperatures from 15°C to 25°C or from 25°C to 60°C, or from 35°C to 50°C or from 20°C to 25°C, or from 30°C to 40°C, or from 25°C to 45°C.
  • the reaction times vary from several minutes to several hours 12 hours, 24 hours or 48 hours.
  • the reactions take place in solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl fe/f-butyl ether (MTBE), dimethylformamide (DMF), and dichloromethane.
  • solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl fe/f-butyl ether (MTBE), dimethylformamide (DMF), and dichloromethane.
  • solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl
  • the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (VII), as shown in Scheme 4, wherein: R 1 , R 2 , R 3 , R 4 , R a , R b , R c , R d , X 1 , X 2 , R k , R e and R f are as defined herein.
  • the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (D) starting with an olefin metathesis catalyst of Formula (VII), as shown in Scheme 5, wherein: R 1 , R 2 , R 3 , R 4 , R a , R b , R c , R d , X 1 , X 2 , R9, R h and R' are as defined herein.
  • the metal carbene olefin metathesis catalysts can be utilized in olefin metathesis reactions according to techniques known in the art.
  • the metal carbene olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension.
  • the metal carbene olefin metathesis catalysts When the metal carbene olefin metathesis catalysts are added to a resin composition as a suspension, the metal carbene olefin metathesis catalysts are suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-/so-propylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction.
  • a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-/so-propylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boil
  • the amount of catalyst that is used i.e., the "catalyst loading" in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading can be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate (e.g., cyclic olefins).
  • an olefinic substrate e.g., cyclic olefins
  • Resin compositions that may be used with the present invention disclosed herein comprise one or more cyclic olefins.
  • Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or polyunsaturated C5 to C24 hydrocarbons that may be mono-, di-, or poly-cyclic.
  • the cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.
  • bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tncyclopentadiene (cyclopentadiene thmer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C2-C12 hydrocarbyl substituted norbornenes; 5-butyl-2-norbornene; 5-hexyl- 2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5- vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-/sopropenyl-2-norbornene; 5-propeny
  • Ultrene® 99 dicyclopentadiene was obtained from Cymetech Corporation.
  • a modified DCPD base resin containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPD generally as described in U.S. Pat. No. 4,899,005.
  • Catalysts C931 , C933, C793, C827, C929, C785ss, C765ss, and C848 were prepared using known methods.
  • GC Method used in Example 9 Column: HP-5, 30m x 0.25mm (ID) x 0.25pm film thickness; Manufacturer: Agilent; GC and column conditions: Injector temperature: 250 °C, Detector temperature: 280 °C; Oven temperature: Starting temperature: 100 °C, hold time: 1 minute; Ramp rate 10 °C/min to 270 °C, hold time: 12 minutes; Carrier gas: Helium; Average velocity: 30 cm/sec; Split ratio: 40.8: 1 .
  • C885JU [00097] To a 20 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), dimorpholino methanethione (0.290 g, 1 .34 mmol), and diethyl ether (10 mL). The reaction was stirred at ambient temperature for 18 hours. The resulting precipitate was isolated by filtration, washed with diethyl ether (3 x 10 mL), hexanes (1 x 10 mL) then dried in vacuum to afford C885TU (0.467 g, 98.3% yield).
  • the conversion to diethyl cyclopent-3-ene-1 , 1 -dicarboxylate was determined by comparing the ratio of the integrals of the methylene protons in the starting material and product ( ⁇ 2.62 (dt) and 3.00 (s) respectively).

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Abstract

La présente invention concerne de façon générale des catalyseurs de métathèse d'oléfines, la préparation de tels composés, des compositions comprenant de tels composés, des procédés d'utilisation de tels composés et l'utilisation de tels composés dans la métathèse d'oléfines et dans la synthèse de catalyseurs de métathèse d'oléfines apparentés. L'invention trouve une utilité dans les domaines de la catalyse, de la synthèse organique, de la chimie des polymères et dans des applications industrielles, telles que le pétrole et le gaz, les produits chimiques fins et les produits pharmaceutiques.
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US11161104B2 (en) 2018-02-13 2021-11-02 Umicore Ag & Co. Kg Reactions of olefin derivatives in the presence of methathesis catalysts
WO2021247583A1 (fr) 2020-06-01 2021-12-09 Provivi, Inc. Synthèse de dérivés de phéromone par métathèse d'oléfines à sélectivité z

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US20140357820A1 (en) * 2013-02-27 2014-12-04 Materia, Inc. Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts
WO2017009232A1 (fr) * 2015-07-10 2017-01-19 Bergen Teknologioverføring As Catalyseurs de métathèse d'oléfines améliorés
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US20140357820A1 (en) * 2013-02-27 2014-12-04 Materia, Inc. Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts
US20170022231A1 (en) * 2015-03-20 2017-01-26 California Institute Of Technology Catalysts for (e)-selective olefin metathesis
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11161104B2 (en) 2018-02-13 2021-11-02 Umicore Ag & Co. Kg Reactions of olefin derivatives in the presence of methathesis catalysts
US11958042B2 (en) 2018-02-13 2024-04-16 Umicore Ag & Co. Kg Reactions of olefin derivatives in the presence of metathesis catalysts
WO2021247583A1 (fr) 2020-06-01 2021-12-09 Provivi, Inc. Synthèse de dérivés de phéromone par métathèse d'oléfines à sélectivité z

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