METATHESIS CATALYSTS

TECHNICAL FIELD

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.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. Recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined olefin metathesis catalysts.

The technology of ruthenium metathesis catalysts has 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).

First Generation Grubbs ruthenium olefin metathesis catalysts, such as: (PCy₃)₂(Cl)₂Ru═CHPh, have been largely used in organic synthesis.

The incorporation of certain types of 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: (IMesH₂)(PCy₃)(Cl)₂Ru═CHPh, where IMesH₂is 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene.

In order to exchange the phosphine on the Second Generation Grubbs ruthenium olefin metathesis catalysts, the Grubbs group reported in 2001 (Organometallics 2001, 20, 5314-5318) a method involving a precursor bearing two pyridine ligands: (IMesH₂)(Cl)₂(C₅H₅N)₂Ru═CHPh. The labile pyridine ligands allow the facile preparation of diverse ruthenium olefin metathesis catalysts. However, the preparation of pyridine complexes, requires large quantities of expensive and malodorous reagents (pyridines), and difficult reaction conditions (negative ° C. temperatures) especially for industrial scale-up.

Therefore there is an ongoing need for efficient, high yield, high purity and ease in scaling up procedures for the synthesis of olefin metathesis catalysts, particularly Second Generation Grubbs ruthenium olefin metathesis catalysts.

SUMMARY OF THE INVENTION

To meet this need the inventors have discovered novel ruthenium olefin metathesis catalysts, bearing a nitrile ligand as described herein. The ruthenium olefin metathesis catalysts bearing nitrile labile ligands have allowed the synthesis of various Second Generation Grubbs ruthenium olefin metathesis catalysts in higher yield and with higher purity, compared to the existing procedures.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (I):

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wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

L¹and L²are independently neutral electron donor ligands;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

R is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R is unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₃-C₈cycloalkyl, substituted C₃-C₈cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄aryl; typically R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹and X²are independently anionic ligands; generally X¹and X²are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio or nitrate; typically X¹and X²are independently Cl, Br, I or F; and

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R¹is hydrogen and typically R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², R′, and R²are optionally linked together to form a cyclic group, including bidentate or multidentate ligands; or any one or more of X¹, X², L¹, L², R′, and R²is/are optionally attached to a support.

In one embodiment, the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.

In one embodiment, the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions.

In one embodiment, the invention provides a method of synthesizing a Second generation Grubbs catalyst, using an olefin metathesis catalyst of the invention.

Other embodiments of the invention are described herein.

These and other aspects of the present invention will be apparent to one of skill in the art, in light of the following detailed description and examples. Furthermore, it is to be understood that none of the embodiments or examples of the invention described herein are to be interpreted as being limiting.

DETAILED DESCRIPTION

Unless otherwise indicated, 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 to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “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.

As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

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:

The term “alkyl” as used herein, 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, iso-propyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. 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 terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein, refers to a divalent linear, branched, or cyclic alkyl group, where “alkyl” is as defined herein.

The term “alkenyl” as used herein, 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, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Generally “alkenyl” groups herein contain 2 to 24 carbon atoms, typically “alkenyl” groups herein contain 2 to 12 carbon atoms. The term “lower alkenyl” intends an “alkenyl” group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic “alkenyl” group, typically 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 terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing “alkenyl” and lower “alkenyl,” respectively. The term “alkenyl” is used interchangeably with the term “olefin” herein.

The term “alkenylene” as used herein, refers to a divalent linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined herein.

The term “alkynyl” as used herein, 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. 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 terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl,” respectively.

The term “alkoxy” as used herein 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 refers to an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

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). “Aryl” groups 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. 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.

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 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. Examples of “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.

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. “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. 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 defined herein.

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 herein.

The terms “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. The term “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.

The terms “halo,” “halogen,” and “halide” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “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. The term “lower hydrocarbyl” intends a “hydrocarbyl” group of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term “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. The term “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. 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.

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” can be monocyclic, bicyclic, or polycyclic as described herein with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, 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, tetrazolyl, etc.

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 referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C₁-C₂₄alkoxy, C₂-C₂₄alkenyloxy, C₂-C₂₄alkynyloxy, C₅-C₂₄aryloxy, C₆-C₂₄aralkyloxy, C₆-C₂₄alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C₂-C₂₄alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄arylcarbonato (—O—(CO)—O-aryl), carboxyl (—COOH), carboxylato (—COO⁻), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂, mono-(C₅-C₂₄aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄aryl)₂), N—(C₁-C₂₄alkyl)-N—(C₅-C₂₄aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄aryl)₂), N—(C₁-C₂₄alkyl)-N—(C₅-C₂₄aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH₂), cyano(—C≡N), cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄alkyl)-substituted amino, di-(C₁-C₂₄alkyl)-substituted amino, mono-(C₅-C₂₄aryl)-substituted amino, di-(C₅-C₂₄aryl)-substituted amino, (C₁-C₂₄alkyl)(C₅-C₂₄aryl)-substituted amino, C₂-C₂₄alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R is hydrogen, C₁-C₂₄alkyl, C₅-C₂₄aryl, C₆-C₂₄alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀alkylimino (—CR═N(alkyl), where R is hydrogen, C₁-C₂₄alkyl, C₅-C₂₄aryl, C₆-C₂₄alkaryl, C₆-C₂₄aralkyl, etc.), arylimino (—CR═N(aryl), where R is hydrogen, C₁-C₂₀alkyl, C₅-C₂₄aryl, C₆-C₂₄alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato (—SO₂—O⁻), C₁-C₂₄alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C₅-C₂₄arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄monoalkylaminosulfonyl —SO₂—N(H) alkyl), C₁-C₂₄dialkylaminosulfonyl —SO₂—N(alkyl)₂, C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆alkyl), C₂-C₂₄alkenyl (preferably C₂-C₁₂alkenyl, more preferably C₂-C₆alkenyl), C₂-C₂₄alkynyl (preferably C₂-C₁₂alkynyl, more preferably C₂-C₆alkynyl), C₅-C₂₄aryl (preferably C₅-C₁₄aryl), C₆-C₂₄alkaryl (preferably C₆-C₁₆alkaryl), and C₆-C₂₄aralkyl (preferably C₆-C₁₆aralkyl).

By “Grubbs-Hoveyda ligands,” it is meant benzylidene ligands having a chelating alkyloxy group attached to the benzene ring at the ortho position.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, it 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.

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 can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

“Optional” or “optionally” means that the subsequently described circumstance can or cannot occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent can or cannot be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Olefin Metathesis Catalysts

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (I):

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wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

Lⁱand L²are independently neutral electron donor ligands;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹is hydrogen and R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene.

In one embodiment of Formula (I), any two or more of X¹, X², L¹, L², R¹, and R²are optionally linked together to form a cyclic group, including bidentate or multidentate ligands; or any one or more of X¹, X², L¹, L², R¹, and R²is/are optionally attached to a support.

In one embodiment the invention provides catalysts, represented by the structure of Formula (I), wherein M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium; m is 0, 1 or 2; typically m is 0; R is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R is unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₃-C₈cycloalkyl, substituted C₃-C₈cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄aryl; X¹and X²are independently anionic ligands; generally X¹and X²are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio or nitrate; typically X¹and X²are independently Cl, Br, I or F; R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹and R²are linked together to form an optionally substituted indenylidene; n is 0, and L¹is independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether (including cyclic ethers), amine, amide, imine, nitrile, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine and thioether; typically L¹is of the formula PR^H1R^H2R^H3, where R^H1, R^H2, and R^H3are each independently substituted or unsubstituted aryl, or substituted or unsubstituted C₁-C₁₀alkyl; typically, R^H1, R^H2, and R^H3are each independently primary alkyl, secondary alkyl, or cycloalkyl.

In one embodiment the invention provides an olefin metathesis catalyst, represented by the structure of Formula (II):

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wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

L¹is a carbene;

L²is a neutral electron donor ligand;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or typically, R¹is hydrogen and R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

X³and X⁴are independently O or S; typically, X³and X⁴are each S; and

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (III),

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wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

L²is a neutral electron donor ligand;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or typically, R¹is hydrogen and R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^3a, N, O, S, or P; only one of X or Y can be C or CR^3a;

typically X and Y are each N;

Q¹, Q², R³, R^3aand R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q¹, Q², R³, R^3aand R⁴are 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 Q¹, Q², R³, R^3aand R⁴are 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.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV),

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wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

L²is a neutral electron donor ligand;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹is hydrogen and R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

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 each N;

R^3ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; generally Q is a two-atom linkage having the structure —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t- or [CR^II═CR¹³]—; typically Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t—, wherein R¹¹, R¹², R¹³, and R¹⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R¹¹, R¹², R¹³and R¹⁴are independently hydrogen, unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₁-C₁₂heteroalkyl, substituted C₁-C₁₂heteroalkyl, unsubstituted phenyl, or substituted phenyl; “s” and “t” are independently 1 or 2; typically “s” and “t” are each 1; or any two of R¹¹, R¹², R¹³, and R¹⁴are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure; and

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently adamantyl, 2,4,6-trimethylphenyl (i.e., mesityl or Mes as defined herein), 2-iso-propyl-phenyl (IPP, Ipp or ipp), 2,6-di-iso-propylphenyl (i.e., DIPP or DiPP as defined herein) or, are 2-iso-propyl-6-methylphenyl (i.e., MIPP, Mipp or MiPP as defined herein).

In one embodiment of Formula (IV), R³and R⁴are independently aromatic, composed of one or two aromatic rings, e.g., R³and R⁴are independently unsubstituted phenyl, substituted phenyl, unsubstituted biphenyl, substituted biphenyl, or the like. As an example, R³and R⁴are each 2,4,6-trimethylphenyl. As another example, R³and R⁴are each 2,6-di-iso-propylphenyl. As another example, R³and R⁴are each 2-iso-propyl-6-methylphenyl. As another example, R³and R⁴are each 2-iso-propyl-phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 1; L²is N≡C—R; m is 0; R is C₁-C₁₀alkyl; X¹and X²are independently Cl, Br, I or F; X and Y are each N; R¹is hydrogen; R²is phenyl or 2-methyl-1-propenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— or —[CR¹¹═CR¹³]— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 1; L²is N≡C—R; m is 0; R is C₁-C₁₀alkyl; X¹and X²are independently Cl, Br, I or F; X and Y are each N; R¹is hydrogen; R²is phenyl or 2-methyl-1-propenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 1; L²is N≡C—R; m is 0; R is CH₃; X¹and X²are each Cl; X and Y are each N; R¹is hydrogen; R²is phenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are each 2,4,6-trimethylphenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 1; L²is N≡C—R; m is 0; R is CH₃; X¹and X²are each Cl; X and Y are each N; R¹and R²form together 3-phenyl-indenylidene; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are each 2,4,6-trimethylphenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 0; m is 0; R is C₁-C₁₀alkyl; X¹and X²are independently Cl, Br, I or F; X and Y are each N; R¹is hydrogen; R²is phenyl or 2-methyl-1-propenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— or —[CR¹¹═CR¹³]— wherein R¹¹, R¹², R¹³and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 0; m is 0; R is C₁-C₁₀alkyl; X¹and X²are independently Cl; X and Y are each N; R¹is hydrogen; R²is phenyl or 2-methyl-1-propenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 0; m is 0; R is C₁-C₁₀alkyl; X¹and X²are independently Cl, Br, I or F; X and Y are each N; R¹is hydrogen; R²is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenyl-1-indenylidene; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³and R¹⁵are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 0; m is 0; R is CH₃; X¹and X²are each Cl; X and Y are each N; R¹is hydrogen; R²is phenyl; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are each 2,4,6-trimethylphenyl.

In one embodiment of Formula (IV), M is ruthenium; n is 0; m is 0; R is CH₃; X¹and X²are each Cl; X and Y are each N; R¹and R²form 3-phenyl-indenylidene; Q is —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— wherein R¹¹, R¹², R¹³and R¹⁴are each hydrogen; and “s” and “t” are each 1; and R³and R⁴are each 2,4,6-trimethylphenyl.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

X¹and X²are independently halogen;

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

X and Y are each N;

Q is —(CH₂—CH₂)— (i.e., a two-atom linkage having the structure —[CR¹¹R¹²]_s— [CR¹³R¹⁴]_t—; wherein R¹¹, R¹², R¹³, and R¹⁴are each hydrogen; and “s” and “t” are each 1);

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R³is unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; and

R⁴is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R⁴is unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide.

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (V):

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wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

R is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R is unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₃-C₈cycloalkyl, substituted C₃-C₈cycloalkyl, unsubstituted C₅-C₂₄aryl or substituted C₅-C₂₄aryl;

X¹and X²are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio or nitrate; typically X¹and X²are independently Cl, Br, I or F; and

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or are 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (V), R¹is hydrogen; R²is phenyl, 2-iso-propyl-phenyl, 2-iso-propoxy-phenyl

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or 2-methyl-1-propenyl (—CH═C(CH₃)₂or

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or R¹and R²are linked together to form 3-phenylinden-1-ylidene

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R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹and X²are each Cl; and

R³and R⁴are independently phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (V) are described in Table (1), wherein X¹is C₁and X²is C₁.

TABLE (1)

Catalyst
R¹
R²
R
R³
R⁴

1
H
Ph
Me
DIPP
DIPP

2
H
Ph
Me
Mes
Mes

3
H
Ph
Me
Mipp
Mipp

4
H
Ph
Et
DIPP
DIPP

5
H
Ph
Et
Mes
Mes

6
H
Ph
Et
Mipp
Mipp

7
H
Ph
Ph
DIPP
DIPP

8
H
Ph
Ph
Mes
Mes

9
H
Ph
Ph
Mipp
Mipp

10
H
Ph
Ph
Ipp
Ipp

11
H

embedded image

Me
DIPP
DIPP

12
H

embedded image

Me
Mes
Mes

13
H

embedded image

Me
Mipp
Mipp

14
H

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Et
DIPP
DIPP

15
H

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Et
Mes
Mes

16
H

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Et
Mipp
Mipp

17
H

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Ph
DIPP
DIPP

18
H

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Ph
Mes
Mes

19
H

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Ph
Mipp
Mipp

20
H

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Ph
Ipp
Ipp

21
H

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Me
DIPP
DIPP

22
H

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Me
Mes
Mes

23
H

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Me
Mipp
Mipp

24
H

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Et
DIPP
DIPP

25
H

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Et
Mes
Mes

26
H

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Et
Mipp
Mipp

27
H

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Ph
DIPP
DIPP

28
H

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Ph
Mes
Mes

29
H

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Ph
Mipp
Mipp

30
H

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Ph
Ipp
Ipp

31

embedded image

Me
DIPP
DIPP

32

embedded image

Me
Mes
Mes

33

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Me
Mipp
Mipp

34

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Et
DIPP
DIPP

35

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Et
Mes
Mes

36

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Et
Mipp
Mipp

37

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Ph
DIPP
DIPP

38

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Ph
Mes
Mes

39

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Ph
Mipp
Mipp

40

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Ph
Ipp
Ipp

wherein: Mes is

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Mipp is

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DIPP is

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and Ipp is

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In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

X¹and X²are independently halogen;

R¹is hydrogen;

X and Y are each N;

Q is —(CH═CH)— (i.e., a two-atom linkage having the structure [CR¹¹═CR¹³]—; wherein R¹¹and R¹³are each hydrogen);

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VI):

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wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R²is phenyl, 2-iso-propylphenyl, 2-iso-propoxy-phenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

R is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R is substituted C₁-C₁₀alkyl, unsubstituted C₁-C₁₀alkyl, unsubstituted C₃-C₈cycloalkyl, substituted C₃-C₈cycloalkyl, substituted C₅-C₂₄aryl or unsubstituted C₅-C₂₄aryl;

X¹and X²are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio or nitrate; typically X¹and X²are independently Cl, Br, I or F; and

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

In one embodiment of Formula (VI) R¹is hydrogen; R²is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenylinden-1-ylidene;

R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹and X²are each Cl; and

R³and R⁴are independently phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VI) are described in Table (2), wherein X¹is C₁and X²is C₁.

TABLE (2)

Catalyst
R¹
R²
R
R³
R⁴

41
H
Ph
Me
DIPP
DIPP

42
H
Ph
Me
Mes
Mes

43
H
Ph
Me
Mipp
Mipp

44
H
Ph
Et
DIPP
DIPP

45
H
Ph
Et
Mes
Mes

46
H
Ph
Et
Mipp
Mipp

47
H
Ph
Ph
DIPP
DIPP

48
H
Ph
Ph
Mes
Mes

49
H
Ph
Ph
Mipp
Mipp

50
H
Ph
Ph
Ipp
Ipp

51
H

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Me
DIPP
DIPP

52
H

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Me
Mes
Mes

53
H

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Me
Mipp
Mipp

54
H

embedded image

Et
DIPP
DIPP

55
H

embedded image

Et
Mes
Mes

56
H

embedded image

Et
Mipp
Mipp

57
H

embedded image

Ph
DIPP
DIPP

58
H

embedded image

Ph
Mes
Mes

59
H

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Ph
Mipp
Mipp

60
H

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Ph
Ipp
Ipp

61
H

embedded image

Me
DIPP
DIPP

62
H

embedded image

Me
Mes
Mes

63
H

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Me
Mipp
Mipp

64
H

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Et
DIPP
DIPP

65
H

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Et
Mes
Mes

66
H

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Et
Mipp
Mipp

67
H

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Ph
DIPP
DIPP

68
H

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Ph
Mes
Mes

69
H

embedded image

Ph
Mipp
Mipp

70
H

embedded image

Ph
Mipp
Mipp

71

embedded image

Me
DIPP
DIPP

72

embedded image

Me
Mes
Mes

73

embedded image

Me
Mipp
Mipp

74

embedded image

Et
DIPP
DIPP

75

embedded image

Et
Mes
Mes

76

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Et
Mipp
Mipp

77

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Ph
DIPP
DIPP

78

embedded image

Ph
Mes
Mes

79

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Ph
Mipp
Mipp

80

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Ph
Ipp
Ipp

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

X¹and X²are independently halogen;

R¹is hydrogen;

Y is N;

X is CR^3a;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t—; R¹¹, R¹², R¹³, and R¹⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R¹¹, R¹², R¹³and R¹⁴are independently hydrogen, unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₁-C₁₂heteroalkyl, substituted C₁-C₁₂heteroalkyl, unsubstituted phenyl, or substituted phenyl;

“s” and “t” are each 1;

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VII):

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wherein:

R¹is hydrogen;

X¹and X²are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio or nitrate; generally X¹and X²are independently Cl, Br, I or F; typically X¹and X²are each Cl;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³is unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl;

R¹¹, R¹², R¹³and R¹⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R¹¹, R¹², R¹³and R¹⁴are independently hydrogen, unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₁-C₁₂heteroalkyl, substituted C₁-C₁₂heteroalkyl, unsubstituted C₄-C₁₂cycloalkyl, substituted C₄-C₁₂cycloalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄heteroaralkyl or substituted C₆-C₂₄heteroaralkyl; typically, R¹¹and R¹²are each methyl and R¹³and R¹⁴are each hydrogen;

R^3ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^3ais unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₄-C₁₂cycloalkyl, substituted C₄-C₁₂cycloalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄heteroaralkyl or substituted C₆-C₂₄heteroaralkyl; typically R^3ais methyl, ethyl, n-propyl, or phenyl; and

R⁴is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴is unsubstituted C₁-C₁₂alkyl, substituted C₁-C₁₂alkyl, unsubstituted C₄-C₁₂cycloalkyl, substituted C₄-C₁₂cycloalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄heteroaralkyl or substituted C₆-C₂₄heteroaralkyl; typically R⁴is methyl, ethyl, n-propyl, or phenyl; or R⁴together with R^3acan form a five- to ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VII) are described in Table (3), wherein X¹is Cl, X²is Cl, R¹¹is methyl, R¹²is methyl, R¹³is hydrogen, R¹⁴is hydrogen and R is methyl.

TABLE (3)

Catalyst
R¹
R²
R³
R^3a
R⁴

81
H
Ph
2-Me—C₆H₅
Me
Me

82
H
Ph
Mes
Me
Me

83
H
Ph
Mipp
Me
Me

84
H
Ph
EMP
Me
Me

85
H
Ph
DIPP
Me
Me

86
H
Ph
IPP
Me
Me

87
H

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2-Me—C₆H₅
Me
Me

88
H

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Mes
Me
Me

89
H

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Mipp
Me
Me

90
H

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EMP
Me
Me

91
H

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DIPP
Me
Me

92
H

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IPP
Me
Me

93
H

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2-Me—C₆H₅
Me
Me

94
H

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Mes
Me
Me

95
H

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Mipp
Me
Me

96
H

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EMP
Me
Me

97
H

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DIPP
Me
Me

98
H

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IPP
Me
Me

99

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2-Me—C₆H₅
Me
Me

100

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Mes
Me
Me

101

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Mipp
Me
Me

102

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EMP
Me
Me

103

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DIPP
Me
Me

104

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IPP
Me
Me

105
H
Ph
2-Me—C₆H₅
Me
Me

106
H
Ph
Mes
Me
Me

107
H
Ph
Mipp
Me
Me

108
H
Ph
EMP
Me
Me

109
H
Ph
DIPP
Me
Me

110
H
Ph
IPP
Me
Me

111
H

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2-Me—C₆H₅
Me
Me

112
H

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Mes
Me
Me

113
H

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Mipp
Me
Me

114
H

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EMP
Me
Me

115
H

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DIPP
Me
Me

116
H

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IPP
Me
Me

117
H

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2-Me—C₆H₅
Me
Me

118
H

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Mes
Me
Me

119
H

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Mipp
Me
Me

120
H

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EMP
Me
Me

121
H

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DIPP
Me
Me

122
H

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IPP
Me
Me

123

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2-Me—C₆H₅
Me
Me

124

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Mes
Me
Me

125

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Mipp
Me
Me

126

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EMP
Me
Me

127

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DIPP
Me
Me

128

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IPP
Me
Me

129
H
Ph
2-Me—C₆H₅
Me
Me

130
H
Ph
Mes
Me
Me

131
H
Ph
Mipp
Me
Me

132
H
Ph
EMP
Me
Me

133
H
Ph
DIPP
Me
Me

134
H
Ph
IPP
Me
Me

135
H

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2-Me—C₆H₅
Me
Me

136
H

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Mes
Me
Me

137
H

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Mipp
Me
Me

138
H

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EMP
Me
Me

139
H

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DIPP
Me
Me

140
H

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IPP
Me
Me

141
H

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2-Me—C₆H₅
Me
Me

142
H

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Mes
Me
Me

143
H

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Mipp
Me
Me

144
H

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EMP
Me
Me

145
H

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DIPP
Me
Me

146
H

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IPP
Me
Me

147

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2-Me—C₆H₅
Me
Me

148

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Mes
Me
Me

149

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Mipp
Me
Me

150

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EMP
Me
Me

151

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DIPP
Me
Me

152

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IPP
Me
Me

wherein EMP is

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In another embodiment of Formula (IV), the invention provides an olefin metathesis catalyst wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium; typically M is ruthenium;

L²is a neutral electron donor ligand;

n is 0 or 1; typically n is 0;

m is 0, 1 or 2; typically m is 0;

X and Y are independently C, CR^3aor N; and only one of X or Y can be C or CR^3a;

R^3ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t— or —[CR¹¹═CR¹³]—;

“s” and “t” are independently 1 or 2;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R⁴is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R¹and R²are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

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the moiety is

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X³and X⁴are independently O or S; and

R^x, R^y, R^wand R^zare independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^x, R^y, R^wand R^zare independently C₁-C₆alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; or R^xand R^yare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wand R^zare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yand R^ware linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In another embodiment of Formula (IV), the invention provides an olefin metathesis catalyst wherein:

M is Ru;

n is 0;

m is 0;

X and Y are each N;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_s—[CR¹³R¹⁴]_t—;

R¹¹, R¹², R¹³, and R¹⁴are independently C₁-C₆alkyl, or hydrogen; generally R¹¹is hydrogen or methyl, R¹²is hydrogen or methyl, R¹³is hydrogen and R¹⁴is hydrogen; typically R¹¹, R¹², R¹³and R¹⁴are each hydrogen;

“s” and “t” are each 1;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R⁴is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R¹is hydrogen and R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

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the moiety is

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X³and X⁴are each S; and

R^x, R^y, R^wand R^zare independently C₁-C₆alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; generally R^xis Me, hydrogen or Cl, R^yis hydrogen, R^wis hydrogen, and R^zis Cl, t-Bu, hydrogen or Ph; or R^xand R^yare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wand R^zare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yand R^ware linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VIII):

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wherein:

R³is unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl or 2-methyl-phenyl;

R⁴is unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R⁴is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl or 2-methyl-phenyl;

R¹is hydrogen and R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene;

R¹¹, R¹², R¹³and R¹⁴are independently C₁-C₆alkyl, or hydrogen; generally R¹¹is hydrogen or methyl, 10²is hydrogen or methyl, R¹³is hydrogen and R¹⁴is hydrogen; typically R¹¹, R¹², R¹³and R¹⁴are each hydrogen; and

R^x, R^y, R^wand R^zare independently C₁-C₆alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; generally R^xis methyl, hydrogen or Cl, R^yis hydrogen, R^wis hydrogen, and R^zis Cl, t-butyl, hydrogen or phenyl; or R^xand R^yare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wand R^zare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yand R^ware linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (VIII), wherein:

R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

R³is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl or 2-methyl-phenyl;

R⁴is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl or 2-methyl-phenyl;

R¹is hydrogen and R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene; and

R^xis methyl, hydrogen or Cl, R^yis hydrogen, R^wis hydrogen, and R^zis Cl, t-butyl, hydrogen or phenyl; or R^xand R^yare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wand R^zare linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yand R^ware linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VIII) are described in Table (4), wherein R is methyl, R^yis hydrogen and R^wis hydrogen.

TABLE (4)

Catalyst
R¹
R²
R³
R⁴
R^x
R^z

153
H
Ph
2-Me—C₆H₅
2-Me—C₆H₅
Cl
Cl

154
H
Ph
Mes
Mes
Cl
Cl

155
H
Ph
Mipp
Mipp
Cl
Cl

156
H
Ph
DIPP
DIPP
Cl
Cl

157
H
Ph
IPP
IPP
Cl
Cl

158
H

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2-Me—C₆H₅
2-Me—C₆H₅
Cl
Cl

159
H

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Mes
Mes
Cl
Cl

160
H

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Mipp
Mipp
Cl
Cl

161
H

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DIPP
DIPP
Cl
Cl

162
H

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IPP
IPP
Cl
Cl

163
H

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2-Me—C₆H₅
2-Me—C₆H₅
Cl
Cl

164
H

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Mes
Mes
Cl
Cl

165
H

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Mipp
Mipp
Cl
Cl

166
H

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DIPP
DIPP
Cl
Cl

167
H

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2-Me—C₆H₅
2-Me—C₆H₅
Cl
Cl

168
H

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Mes
Mes
Cl
Cl

169
H

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Mipp
Mipp
Cl
Cl

170
H

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DIPP
DIPP
Cl
Cl

171
H

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IPP
IPP
Cl
Cl

172
H

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IPP
IPP
Cl
Cl

173

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2-Me—C₆H₅
2-Me—C₆H₅
Cl
Cl

174

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Mes
Mes
Cl
Cl

175

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Mipp
Me
Cl
Cl

176

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DIPP
DIPP
Cl
Cl

177

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IPP
Me
Cl
Cl

178
H
Ph
2-Me—C₆H₅
2-Me—C₆H₅
H
Ph

179
H
Ph
Mes
Mes
H
Ph

180
H
Ph
Mipp
Mipp
H
Ph

181
H
Ph
DIPP
DIPP
H
Ph

182
H
Ph
IPP
IPP
H
Ph

183
H

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2-Me—C₆H₅
2-Me—C₆H₅
H
Ph

184
H

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Mes
Mes
H
Ph

185
H

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Mipp
Mipp
H
Ph

186
H

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DIPP
DIPP
H
Ph

187
H

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IPP
IPP
H
Ph

188
H

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2-Me—C₆H₅
2-Me—C₆H₅
H
Ph

189
H

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Mes
Mes
H
Ph

190
H

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Mipp
Mipp
H
Ph

191
H

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DIPP
DIPP
H
Ph

192
H

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IPP
IPP
H
Ph

193

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2-Me—C₆H₅
2-Me—C₆H₅
H
Ph

194

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Mes
Mes
H
Ph

195

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Mipp
Mipp
H
Ph

196

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DIPP
DIPP
H
Ph

197

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IPP
IPP
H
Ph

198
H
Ph
2-Me—C₆H₅
2-Me—C₆H₅
Me
t-Bu

199
H
Ph
Mes
Mes
Me
t-Bu

200
H
Ph
Mipp
Mipp
Me
t-Bu

201
H
Ph
DIPP
DIPP
Me
t-Bu

202
H
Ph
IPP
IPP
Me
t-Bu

203
H

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2-Me—C₆H₅
2-Me—C₆H₅
Me
t-Bu

204
H

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Mes
Mes
Me
t-Bu

205
H

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Mipp
Mipp
Me
t-Bu

206
H

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DIPP
DIPP
Me
t-Bu

207
H

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IPP
IPP
Me
t-Bu

208
H

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2-Me—C₆H₅
2-Me—C₆H₅
Me
t-Bu

209
H

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Mes
Mes
Me
t-Bu

210
H

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Mipp
Mipp
Me
t-Bu

211
H

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DIPP
DIPP
Me
t-Bu

212
H

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IPP
IPP
Me
t-Bu

213

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2-Me—C₆H₅
2-Me—C₆H₅
Me
t-Bu

214

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Mes
Mes
Me
t-Bu

215

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Mipp
Mipp
Me
t-Bu

216

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DIPP
DIPP
Me
t-Bu

217

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IPP
IPP
Me
t-Bu

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 made.

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In a typical procedure, an olefin metathesis catalyst of general Formula (A) is reacted at room temperature with tosyl chloride (TsCl) and an excess of nitrile derivative (RCN) to produce an olefin metathesis catalyst of general Formula (V), wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R²is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene; typically R²is phenyl, 2-iso-propoxy-phenyl, 2-iso-propylphenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenyl-1-indenylidene;

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propylphenyl or 2-iso-propyl-6-methyl phenyl; and

R^a, R^b, and R^care each independently substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄aryl or substituted C₁-C₁₀alkyl, unsubstituted C₁-C₁₀alkyl; generally R^a, R^b, and R^care each independently unsubstituted C₅-C₂₄aryl; typically R^a, R^b, and R^care each phenyl.

In another embodiment, 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 nitrile labile 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 higher yield and with higher purity, which presents an advantage compared to the existing synthetic procedures.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (F) starting with an olefin metathesis catalyst of Formula (IV).

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In a typical procedure as shown in Scheme 2, the nitrile ligand of the olefin metathesis catalyst represented by Formula (IV) can be exchanged with a “L” ligand, which is a neutral electron donor. “L” is selected from the group consisting of sulphonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, carbonyl, nitrosyl, pyridine, thioether, Grubbs-Hoveyda ligands, trimethylphosphine (PMe₃), triethylphosphine (PEt₃), tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃), tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine (PCp₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃), trioctylphosphine (POct₃), tri-iso-butylphosphine, (PQ-Bu)₃), triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃), methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), diethylphenylphosphine (PEt₂Ph), phosphabicycloalkane (e.g., monosubstituted 9-phosphabicyclo-[3.3.1]nonane, monosubstituted 9-phosphabicyclo[4.2.1]nonane], cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban), pyridine, 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-di-iso-propylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, carbazole, sulfur-containing heterocycles (e.g., thiophene, 1,2-dithiole, 1,3-dithiol e, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, thioanthrene), oxygen-containing heterocycles (e.g., 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-di oxan, dibenzofuran), mixed (e.g., isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine), and aromatic nitrogen-containing and oxygen-containing heterocycles, monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents.

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. Generally the reactions take place in solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl tert-butyl ether (MTBE), dimethylformamide (DMF), and dichloromethane.

In one embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (B) starting with an olefin metathesis catalyst of Formula (V).

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In a typical procedure, as shown in Scheme 3, the nitrile ligand of the olefin metathesis catalyst represented by Formula (V) is exchanged with a PR^dR^eOR^fligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

R¹is hydrogen;

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl;

R^dis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally R^dis unsubstituted C₁-C₁₀alkyl or unsubstituted C₆-C₁₀aryl; typically R^dis phenyl;

R^eis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally R^eis unsubstituted C₁-C₁₀alkyl or unsubstituted C₆-C₁₀aryl; typically R^eis phenyl; and

R^fis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally R^fis unsubstituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl or unsubstituted C₆-C₁₀aryl; typically R^fis phenyl, methyl or p-(OMe)phenyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (V).

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In a typical procedure as shown in Scheme 4, the nitrile ligand of the olefin metathesis catalyst represented by Formula (V) can be exchanged with a PR^gOR^hOR^jligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene; typically R²is phenyl, 2-iso-propoxy-phenyl, 2-iso-propylphenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenyl-1-indenylidene;

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl;

R^gis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally R^gis unsubstituted C₁-C₁₀alkyl or unsubstituted C₆-C₁₀aryl; typically R^gis phenyl;

R^his unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally R^his unsubstituted C₁-C₁₀alkyl or unsubstituted C₆-C₁₀aryl; typically R^his phenyl or methyl; and

Rⁱis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, unsubstituted C₆-C₁₀aryl, substituted C₆-C₁₀aryl, unsubstituted C₃-C₈cycloalkyl or substituted C₃-C₈cycloalkyl; generally Rⁱis unsubstituted C₁-C₁₀alkyl or unsubstituted C₆-C₁₀aryl; typically Rⁱis phenyl or methyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (D) starting with an olefin metathesis catalyst of Formula (V).

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In a typical procedure as shown in Scheme 5, the acetonitrile ligand of the olefin metathesis catalyst represented by Formula (V) is exchanged with a ligand at 60° C. in ethyl acetate, wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene; typically R²is phenyl, 2-iso-propylphenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenyl-1-indenylidene;

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl;

R^kis hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^s₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R^kis hydrogen;

R¹is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^s2, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R¹is hydrogen;

R^mis hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^s₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R^mis hydrogen, —NO₂, —CN, —CF₃, —SO₂NR^s₂, —NHC(O)CF₃, —NHC(O)C₆F₅, or —NHC(O)OtBu; specifically R^mis hydrogen;

Rⁿis hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^s2, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically Rⁿis hydrogen;

R^sis hydrogen or C₁-C₆alkyl; typically R^sis hydrogen, methyl, ethyl or n-propyl; and

R^qis unsubstituted hydrocarbyl, substituted hydrocarbyl; generally R^qis C₁-C₁₀alkyl; typically R^qis iso-propyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (E) starting with an olefin metathesis catalyst of Formula (V).

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In a typical procedure as shown in Scheme 6, the nitrile ligand of the olefin metathesis catalyst represented by Formula (V) can be exchanged with a P(R^q)₃ligand at room temperature in an inert solvent, such as dichloromethane; wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R²is phenyl, substituted phenyl or substituted 1-propenyl; or R¹and R²are linked together to form an optionally substituted indenylidene; typically R²is phenyl, 2-iso-propylphenyl or 2-methyl-1-propenyl; or R¹and R²are linked together to form 3-phenyl-1-indenylidene;

R³and R⁴are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³and R⁴are independently unsubstituted C₃-C₁₀cycloalkyl, substituted C₃-C₁₀cycloalkyl, unsubstituted C₅-C₂₄aryl, or C₅-C₂₄aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀alkyl, substituted C₁-C₂₀alkyl, unsubstituted C₁-C₂₀heteroalkyl, substituted C₁-C₂₀heteroalkyl, unsubstituted C₅-C₂₄aryl, substituted C₅-C₂₄aryl, unsubstituted C₅-C₂₄heteroaryl, substituted C₅-C₂₄heteroaryl, unsubstituted C₆-C₂₄aralkyl, substituted C₆-C₂₄aralkyl, unsubstituted C₆-C₂₄alkaryl, substituted C₆-C₂₄alkaryl and halide; typically, R³and R⁴are independently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl or 2-iso-propyl-6-methyl phenyl; and

R^qis unsubstituted C₁-C₁₀alkyl, substituted C₁-C₁₀alkyl, substituted C₆-C₁₀aryl, unsubstituted C₆-C₁₀aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈cycloalkyl; generally R^qis substituted C₆-C₁₀aryl, unsubstituted C₆-C₁₀aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈cycloalkyl; typically R^qis phenyl, cyclohexyl, or cyclopentyl.

At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention can be prepared by performing various common chemical reactions. Details of certain specific chemical transformations are provided in the examples.

The metal carbene olefin metathesis catalysts can be utilized in olefin metathesis reactions according to techniques known in the art. For example, the metal carbene olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension. 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-iso-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. It will be appreciated that 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).

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 poly-unsaturated C₅to C₂₄hydrocarbons 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.

Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C₂-C₁₂hydrocarbyl 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-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenyl norbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene; bicyclo[2.2.1]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxy carbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyl tetracyclododecene; 8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene; 8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexylester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; 2-hydroxyethyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; bicyclo[2.2.1] hept-5-ene-2-methanol; bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester; bicyclo[2.2.1] hept-5-ene-2-hexanoic acid-methyl ester; 1,4:5,8-dimethanonaphthalene, 2-hexyl-1,2,3,4,4a,5, 8, 8a-octahydro; bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; 1,4:5,8-dimethano naphthalene; 2-butyl-1,2,3,4,4a,5,8,8a-octahydro; ethylidenetetracyclododecene; 2-vinyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethano naphthalene; and the like, and their structural isomers, stereoisomers, and mixtures thereof.

Experimental
General Information Materials and Methods

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. The examples are to be considered as not being limiting of the invention described herein.

All reactions involving metal complexes were conducted in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commercially available reagents were used as received unless otherwise noted. Silica gel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

Catalysts C931 and C848 were prepared using known methods.

¹H and ¹³C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are reported in ppm downfield from Me₄Si by using the residual solvent peak as an internal standard (CDCl₃δ 7.24 ppm; CD₂Cl₂δ 5.32 ppm). ³¹P NMR used an external standard of 85% H₃PO₄, referenced to 0 ppm. Spectra were analyzed and processed using MestReNova software.

The GC analyses were run using a flame ionization detector. The Column used is: HP-5 from J&W, 30 m-0.25 mm i.d.-0.25 μm film thickness. GC method conditions: injection temperature, 250° C.; detector temperature, 280° C.; oven temperature, starting temperature, 100° C.; hold time, 1 min. The ramp rate was 10° C./min to 250° C., hold time 12 min; carrier gas helium.

The following abbreviations are used in the examples:

mL milliliter
CD₂Cl₂deuterated dichloromethane
DCM dichloromethane
C₆D₆deuterated benzene
Et₂O diethylether
CDCl₃deuterated chloroform
C931

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- [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (phenylindenylidene)(triphenyiphosphine)ruthenium(II) [CAS 340810-50-6]

C848

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- Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine) ruthenium(II) [CAS 246047-72-3]

MeCN acetonitrile

CuCl cooper (I) chloride

MTBE methyl-tert-butyl ether

PCy₃tricyclohexylphosphine

EtOAc ethyl acetate

THMP/IPA tris(hydroxymethyl)phosphine/isopropanol

EXAMPLES
Example 1

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To a 250 mL round bottom flask equipped with a magnetic stir bar was added C931 (20.0 g, 21.48 mmol), acetonitrile (100 mL), and tosyl chloride (2.05 g, 10.74 mmol). The resulting reaction was allowed to stir for 60 minutes at ambient temperature then devolatilized. The resulting residue was recrystallized from MeCN/MTBE at ambient temperature. The red/brown crystals were isolated by filtration and washed with MeCN/MTBE (1:9, 2×25 mL) followed by MTBE (20 mL) then dried in vacuum to afford C710 (14.49 g, 95% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.65 (d, J=6.4 Hz, 1H), 7.72-7.68 (m, 2H), 7.55-7.44 (m, 3H), 7.28-7.23 (m, 3H), 7.19-7.04 (m, 2H), 6.53-6.07 (m, 3H), 4.19-3.94 (m, 4H), 2.67-1.73 (m, 21H).

Example 2

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To a MeCN suspension (10 mL) of C848 (200 mg, 0.236 mmol) was added solid CuCl (46.6 mg, 0.471 mmol) in one portion. The mixture was allowed to stir at ambient temperature for 3 h, during which the solution slowly turned dark green/brown. All volatiles were removed under reduced pressure, and 10 mL of DCM were added. The mixture was passed through a short plug of Celite to remove the unwanted solid. The solvent was then removed under reduced pressure to afford a purple/brown solid of C₆₅₁which was washed with Et₂O, and dried under vacuum (145 mg, 95%).

¹H NMR (300 MHz; CD₂Cl₂): δ 16.66 (s, 1H), 7.63 (t, 1H, 7.9 Hz), 7.34-7.22 (m, 4H), 7.06 (s, 4H), 4.21 (s, 4H), 2.48 (s, 6H), 2.42 (s, 6H), 2.30 (s, 12H).

Example 3

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To a 40 mL scintillation vial equipped with a magnetic stir bar was added C710 (0.500 g, 0.705 mmol), (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.259 g, 0.775 mmol), and tetrahydrofuran (5 mL). The reaction was stirred at ambient temperature for one hour then concentrated to dryness. The resulting residue was extracted with dichloromethane (20 mL), passed through a 0.2 μm syringe filter, and then concentrated in vacuum to ca. 5 mL. Diethyl ether (35 mL) was added slowly affording a black microcrystalline precipitate. The product was isolated by filtration, washed with diethyl ether (2×4 mL) and dried in vacuum to afford C848_ss(0.451 g, 75.4% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 7.84 (d, J=5.8 Hz, 1H), 7.71 (br s, 2H), 7.46 (br s, 3H), 7.16-6.78 (m, 7H), 6.63 (br s, 3H), 4.00 (s, 4H), 2.53 (br s, 6H), 2.39 (s, 3H), 2.27 (br s, 6H), 2.06 (br s, 6H).

Synthesis of Second Generation Grubbs Ruthenium Olefin Metathesis Catalysts

Example 4

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To a 250 mL round bottom flask equipped with a magnetic stir bar was added C710 (7.19 g, 10.12 mmol), dichloromethane (38 mL), and P(PhO)(Ph)₂([CAS 13360-92-4] 2.84 g, 10.20 mmol). The resulting reaction was allowed to stir for 15 minutes at ambient temperature then devolatilized. The resulting residue was triturated with hexanes (100 mL) at ambient temperature. The red/brown powder was isolated by filtration and washed with hexanes (50 mL) then dried in vacuum to afford C947 (9.66 g, 93% yield). The ¹H NMR data correspond to the data found in the literature.

Example 5

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To a 20 mL scintillation vial equipped with a magnetic stir bar was added C710 (0.5 g, 0.70 mmol), dichloromethane (10 mL), and P(MeO)(Ph)₂([CAS 4020-99-9] 0.16 g, 0.74 mmol). The resulting reaction was allowed to stir for 15 minutes at ambient temperature then devolatilized. The resulting residue was triturated with hexanes (10 mL) at ambient temperature. The red/brown powder was isolated by filtration and washed with hexanes (10 mL) then dried in vacuum to afford C885 (0.59 g, 95% yield). The ¹H NMR data correspond to the data found in the literature.

Example 6

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To a 250 mL round bottom flask equipped with a magnetic stir bar was added C710 (5.0 g, 7.04 mmol), dichloromethane (100 mL), and P(OPh-pOMe)(Ph)₂([CAS 1346671-90-6] 2.34 g, 7.59 mmol). The resulting reaction was allowed to stir for 15 minutes at ambient temperature then devolatilized. The resulting residue was triturated with hexanes (100 mL) at ambient temperature. The red/brown powder was isolated by filtration and washed with hexanes (50 mL) then dried in vacuum to afford C977 (6.6 g, 96% yield). The 41 NMR data correspond to the data found in the literature.

Example 7

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To a 20 mL scintillation vial equipped with a magnetic stir bar was added C710 (0.5 g, 0.70 mmol), dichloromethane (10 mL), and PCy₃(0.2 g, 0.71 mmol). The resulting reaction was allowed to stir for 15 minutes at ambient temperature then devolatilized. The resulting residue was triturated with hexanes (10 mL) at ambient temperature. The red/brown powder was isolated by filtration and washed with hexanes (10 mL) then dried in vacuum to afford C949 (0.65 g, 98% yield). The ¹H NMR data correspond to the data found in the literature.

Example 8

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To a 20 mL scintillation vial equipped with a magnetic stir bar was added C710 (0.5 g, 0.70 mmol), dichloromethane (10 mL), and P(Ph)(OMe)₂([CAS 2946-61-4] 0.12 g, 0.73 mmol). The resulting reaction was allowed to stir for 15 minutes at ambient temperature then devolatilized. The resulting residue was triturated with hexanes (10 mL) at ambient temperature. The red/brown powder was isolated by filtration and washed with hexanes (10 mL) then dried in vacuum to afford C834 (0.54 g, 92% yield). The ¹H NMR data correspond to the data found in the literature.

Example 9

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To a 20 mL scintillation vial equipped with a magnetic stir bar was added C710 (0.5 g, 0.70 mmol), ethyl acetate (10 mL), and 2-iso-propoxy-β-methylstyrene (0.18 g, 1.02 mmol). The resulting reaction was allowed to stir for 30 minutes at 60° C. temperature then devolatilized. The resulting residue was triturated with methanol (10 mL) at ambient temperature. The green crystalline material was isolated by filtration and washed with methanol (10 mL) then dried in vacuum to afford C627 (0.37 g, 85% yield). The ¹H NMR data correspond to the data found in the literature.

Catalytic Activity of the Olefin Metathesis Catalysts of the Invention

The catalytic activity of the complexes according to the invention, was evaluated in metathesis reactions as follows.

Example 10

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The ethenolysis reaction was carried out using research grade methyl oleate (>99%) that was purified by storage over activated alumina followed by filtration. The reaction was set up in a glovebox under an atmosphere of argon. Methyl oleate (5.0 g; 6.8 mmol) and a C710 catalyst solution (19.2 μL; 0.035 M; 100 ppm) were added to a Fisher-Porter vessel equipped with a stir bar and pressure head. The vessel was sealed with the pressure head, removed from the glovebox, and then attached to an ethylene source (99.995% pure). The vessel was purged with ethylene at 40° C. Then, the vessel was pressurized to 150 psig with ethylene and the reaction was allowed to proceed at 40° C. for 4 hours. Next, the reaction was cooled to room temperature and the ethylene was completely vented. 1 mL aliquot of the reaction mixture was removed, quenched with 0.1 mL 1M THMP/IPA solution, heated to 70° C. for 1 hour, and then partitioned between hexane and water (1:2 v/v; 3 mL). The organic phase was analyzed by GC. The experiment was repeated with C710 at 1000 ppm (192 μL; 0.035 M) and with C710 at 10000 ppm (0.048 g; 0.067 mmol) catalyst loading. The results are shown in Table (5).

TABLE (5)

GC retention times and response factors

relative to internal standard dodecane (2)

Catalyst

Self-

loading
(1)
(2)
(3)
(5)
(4)
Ethenolysis
Metathesis

(ppm)
(%)
(%)
(%)
(%)
(%)
Yield (%)
Yield (%)

100
45.0
5.1
4.9
22.6
22.5
10.0
45.1

1000
43.7
6.2
6.1
22.0
22.0
12.3
44.0

10000
23.2
26.8
26.2
11.7
11.8
53.0
23.5

Example 11

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The hexenolysis reaction was carried out using soybean oil which, was purified by thermal (200° C.) treatment and storage over activated alumina followed by filtration. The reaction was set up in a glovebox under an atmosphere of argon. The soybean oil (1.0 g; 1.2 mmol) and the catalyst solution (14.8 μL, 0.0352 M; 100 ppm) were added to a 20 mL septa vial equipped with stir bar. The vial was sealed, removed from the glovebox and then attached via PTFE tube to a bubbler. The reaction was allowed to proceed at 40° C. for 4 hours. The reaction was quenched with 0.2 mL 1M THMP/IPA solution and heated to 60° C. for 1 hour. Next, an aliquot of the reaction crude was trans-esterified with 1 mL of 0.1% sodium methoxide in methanol solution. Then, the reaction mixture was partitioned between water and hexanes (1:1 v/v; 2 mL). The organic phase was analyzed by GC.

Example 12

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In an argon filled glovebox, a 40 mL scintillation vial containing a stir bar was charged with C710 (7.4 mg, 0.01 mmol), toluene (5 mL) and diethyl diallylmalonate (0.25 g, 1.04 mmol, GC retention time is 7.299 min). The mixture was heated at 50° C. while monitoring the conversion of diethyl diallylmalonate by GC. After 1 h the GC trace indicated complete conversion to the desired cyclopentene product (GC retention time is 6.426 min).

Example 13

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In an argon filled glovebox, a 4 mL vial containing a stir bar was charged with methyl oleate (0.500 g, 1.69 mmol, GC retention time is 15.268 min) and C710 (61 μL, of a 0.003 M stock solution in DCM, 0.0002 mmol). The reaction mixture was stirred at ambient temperature while monitoring the conversion of methyl oleate by GC. After 1 h the GC trace indicated the reaction had reached complete equilibration with a composition of 25% dimethyl 9-octadecene-1,18-dioate (GC retention time is 18.283 min), 25% 9-octadecene (GC retention time is 11.782 min) and 50% methyl oleate (GC retention time is 15.270 min).

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