Metal Carbene Olefin Metathesis Catalysts

Abstract

The present inventors have discovered various metal carbene olefin metathesis catalysts of the present invention, which are described herein. The present invention relates generally to metal carbene olefin metathesis catalyst compounds, the preparation of such compounds, compositions containing such compounds, methods of using such compounds, articles of manufacture containing such compounds, and the use of such compounds in the metathesis reactions of olefins and olefinic compounds. The present invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and the industrial and fine chemical industries.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 62 / 222,989, filed September 24, 2015, the contents of which are incorporated herein by reference.

[0002] The present invention relates generally to metal carbene olefin metathesis catalyst compounds, the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis reactions of olefins and olefinic compounds. The present invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and the industrial and fine chemical industries. [Background technology]

[0003] In recent years, olefin metathesis reactions using metathesis catalysts have become one of the most useful tools in organic chemistry. A wide variety of ruthenium metathesis catalysts with monodentate mixed ligand systems, such as N-heterocyclic carbene (NHC) / phosphine mixed ligand systems, have been known and investigated. Some examples are shown in Scheme 1. The advantages of ruthenium metathesis catalysts with monodentate NHC / phosphine mixed ligand systems are well known in the art. [ka]

[0004] One particularly important olefin metathesis reaction is ring-opening metathesis polymerization (ROMP). The formation of thermosetting polymers by ROMP is a technically and commercially important processing technique. In this technique, liquid monomers (e.g., at least one cyclic olefin) and a polymerization catalyst (e.g., at least one metal carbene olefin metathesis catalyst) are mixed to form a ROMP composition, which is then poured, cast, or injected into a mold. Polymerization proceeds and, once complete, the molded part is removed from the mold for any required post-cure treatment. The ROMP composition may optionally contain added modifiers, fillers, additives, reinforcing agents, pigments, and the like.

[0005] Unfortunately, little research has been published on ruthenium metathesis catalysts having monodentate mixed ligand systems other than NHC / phosphine mixed ligand systems. Furthermore, many of the known ruthenium metathesis catalysts having NHC / phosphine mixed ligand systems have characteristics that, in some cases, limit their use in specific applications and olefin metathesis reactions. Therefore, there is a continuing need for metal carbene olefin metathesis catalysts, particularly ruthenium metathesis catalysts containing monodentate mixed ligand systems, with improved characteristics that further enable their use in a wider range of applications and olefin metathesis reactions. Summary of the Invention [Problem to be solved by the invention]

[0006] To meet this need, the present inventors have discovered various inventive metal carbene olefin metathesis catalysts described herein. [Means for solving the problem]

[0007] In one embodiment, the present invention provides a metal carbene olefin metathesis catalyst of the present invention, comprising a Group 8 transition metal complex having the structure of formula (I): [ka] During the ceremony, L 1 is a carbene ligand having the structure of formula (II): [ka] M is a Group 8 transition metal, specifically ruthenium or osmium, more specifically ruthenium; X and Y are independently CH, C, N, O, S or P, preferably both X and Y are N; Q 1 , Q 2 , Q 3 and Q 4 is independently a linker, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, e.g., substituted alkylene and / or heteroatom-containing alkylene) or —(CO)—; Q 1 , Q 2 , Q 3 and Q 4 two or more substituents on adjacent atoms in may be joined to form an additional cyclic group; p and q are independently 0, 1, or 2; w, x, y and z are independently 0 or 1, preferably w, x, y and z are 0; R 3 , R 3A , R 4 and R 4A are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl; L 2 is a phosphinite or phosphonite ligand, X 1 and X 2 are independently an anionic ligand and are bonded to M in a trans or cis configuration; m is 0, 1 or 2; R 1 and R 2are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), however, When X is O or S, p is 0; When X is N, CH or P, p is 1; When X is C, p is 2; when Y is O or S, q is 0; when Y is N, CH or P, q is 1; When Y is C, q is 2; and only one of X or Y is C or CH; The catalyst of formula (I) is provided that it does not have the following structure: [ka]

[0008] In one embodiment, the present invention provides a ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin.

[0009] In one embodiment, the present invention provides a ROMP composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and with the proviso that the at least one metal carbene olefin metathesis catalyst is [ka] The condition is that it is not.

[0010] In one embodiment, the present invention provides an article of manufacture comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin.

[0011] In one embodiment, the present invention provides an article of manufacture comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin; and wherein the at least one metal carbene olefin metathesis catalyst is [ka] The condition is that it is not.

[0012] In one embodiment, the present invention provides the use of at least one metal carbene olefin metathesis catalyst in a ROMP reaction.

[0013] In one embodiment, the present invention provides the use of at least one metal carbene olefin metathesis catalyst in a ROMP reaction, wherein the at least one metal carbene olefin metathesis catalyst is [ka] The condition is that it is not.

[0014] Other embodiments of the invention are described herein.

[0015] The metal carbene olefin metathesis catalysts of the present invention are particularly useful in ring-opening metathesis polymerization reactions, but may also find use in other metathesis reactions, such as ring-opening cross-metathesis reactions, cross-metathesis reactions, ring-closing metathesis reactions, self-metathesis reactions, ethenolysis reactions, alkenolysis reactions, or acyclic diene metathesis polymerization reactions, and combinations of such metathesis reactions. These and other aspects of the present invention will become apparent to those skilled in the art from the following detailed description and examples. Furthermore, it is to be understood that any embodiments or examples of the present invention described herein are not to be construed as limiting. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a graph showing the percentage of cis-C885 compared to trans-C885 in CD2Cl2 solution. [Figure 2] 1 is a graph showing the percentage of trans-C947 or cis-C947 in C6D6 or CD2Cl2 solutions. DETAILED DESCRIPTION OF THE INVENTION

[0017] Unless otherwise specified, this invention is not limited to particular reactants, substituents, catalysts, or reaction conditions, etc., as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0018] As used in this 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 α-olefin" includes a single α-olefin as well as combinations or mixtures of two or more α-olefins; reference to "a substituent" encompasses a single substituent as well as two or more substituents, and so forth.

[0019] As used in this specification and the appended claims, the terms "for example," "for example," "such as," or "including" are meant to introduce examples that further clarify the more general subject matter. Unless otherwise expressly stated, these examples are provided solely as an aid in the understanding of the invention and are not meant to be limiting in any way.

[0020] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings.

[0021] The term "alkyl," as used herein, typically, although not necessarily, refers to a straight-chain, branched-chain, or cyclic saturated hydrocarbon group containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), and decyl, and cycloalkyl groups such as cyclopentyl (Cp) and cyclohexyl (Cy). Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term "lower alkyl" refers to an alkyl group of 1 to 6 carbon atoms, and the specific term "cycloalkyl" refers to a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term "substituted alkyl" refers to an alkyl that is substituted with one or more substituents, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to an alkyl in which at least one carbon atom has been replaced with a heteroatom. Unless otherwise specified, the terms "alkyl" and "lower alkyl" include straight-chain, branched-chain, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl, respectively.

[0022] The term "alkylene," as used herein, refers to a divalent straight, branched, or cyclic alkyl group, where "alkyl" is defined above.

[0023] As used herein, the term "alkenyl" refers to a straight-chain, branched-chain, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, and tetracosenyl. Preferred alkenyl groups herein contain 2 to about 12 carbon atoms. The term "lower alkenyl" refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term "cycloalkenyl" preferably refers to a cyclic alkenyl group having 5 to 8 carbon atoms. The term "substituted alkenyl" refers to an alkenyl substituted with one or more substituents, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to an alkenyl in which at least one carbon atom has been replaced with a heteroatom. Unless otherwise specified, the terms "alkenyl" and "lower alkenyl" include straight-chain, branched, cyclic, unsubstituted, substituted and / or heteroatom-containing alkenyl and lower alkenyl, respectively.

[0024] The term "alkenylene," as used herein, refers to a divalent straight, branched, or cyclic alkenyl group, where "alkenyl" is defined above.

[0025] As used herein, the term "alkynyl" refers to a straight- or branched-chain hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl and n-propynyl. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term "lower alkynyl" refers to an alkynyl group of 2 to 6 carbon atoms. The term "substituted alkynyl" refers to an alkynyl group substituted with one or more substituents, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to an alkynyl group in which at least one carbon atom has been replaced with a heteroatom. Unless otherwise specified, the terms "alkynyl" and "lower alkynyl" include straight-chain, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

[0026] The term "alkynylene," as used herein, refers to a divalent alkynyl group, where "alkynyl" is defined above.

[0027] The term "alkoxy" as used herein refers to an alkyl group bonded 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. Similarly, "alkenyloxy" and "lower alkenyloxy" refer to alkenyl and lower alkenyl groups, respectively, bonded through a single terminal ether linkage, and "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups, respectively, bonded through a single terminal ether linkage.

[0028] As used herein, unless otherwise specified, the term "aryl" refers to an aromatic substituent containing one aromatic ring or multiple aromatic rings fused together, directly linked, or indirectly linked (thus different aromatic rings are bonded to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, such as phenyl (Ph), naphthyl, biphenyl, diphenyl ether, diphenylamine, and benzophenone. "Substituted aryl" refers to an aryl moiety substituted with one or more substituents, and the terms "heteroatom-containing aryl" and "heteroaryl" refer to an aryl substituent in which at least one carbon atom has been replaced with a heteroatom, as described in more detail below.

[0029] The term "aryloxy," as used herein, refers to an aryl group bonded through a single, terminal ether linkage, where "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, but are not limited to, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, and 3,4,5-trimethoxy-phenoxy.

[0030] The term "alkaryl" refers to an aryl group containing an alkyl substituent, and the term "aralkyl" refers to an alkyl group containing an aryl substituent, where "aryl" and "alkyl" are defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, with particularly preferred alkaryl and aralkyl groups containing 6 to 16 carbon atoms. Alkaryl groups include, but are not limited to, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, and 3-ethylcyclopenta-1,4-diene. Examples of aralkyl groups include, but are not limited to, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, and 4-benzylcyclohexylmethyl. The terms "alkaryloxy" and "aralkyloxy" refer to a substituent of the formula -OR, respectively, where R is alkaryl or aralkyl as defined above.

[0031] The term "acyl" refers to a substituent having the formula -(CO)-alkyl, -(CO)-aryl, -(CO)-aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl, and the term "acyloxy" refers to a substituent having the formula -O(CO)-alkyl, -O(CO)-aryl, -O(CO)-aralkyl, -O(CO)-alkaryl, -O(CO)-alkenyl, or -(CO)-alkynyl, where "alkyl," "aryl," "aralkyl," "alkaryl," "alkenyl," and "alkynyl" are as defined above. The acetoxy group (-O(CO)CH; often abbreviated as OAc) is a common example of an acyloxy group.

[0032] The terms "cyclic" and "ring" refer to an alicyclic or aromatic group which may be monocyclic, bicyclic, or polycyclic, which may or may not be substituted and / or which may or may not contain heteroatoms. The term "alicyclic" is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, which may be monocyclic, bicyclic, or polycyclic.

[0033] The terms "halo" and "halogen" and "halide" are used in the conventional sense to refer to a fluoro, chloro, bromo or iodo substituent.

[0034] "Hydrocarbyl" refers to monovalent hydrocarbyl groups, such as alkyl, alkenyl, alkynyl, and aryl groups, containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, and most preferably 1 to about 12 carbon atoms, including straight-chain, branched-chain, cyclic, saturated, and unsaturated forms. The term "lower hydrocarbyl" refers to hydrocarbyl groups of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term "hydrocarbylene" refers to divalent hydrocarbyl moieties containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, and most preferably 1 to about 12 carbon atoms, including straight-chain, branched, cyclic, saturated, and unsaturated forms. The term "lower hydrocarbylene" refers to hydrocarbylene groups of 1 to 6 carbon atoms. "Substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituents, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyls in which at least one carbon atom has been replaced with a heteroatom. Similarly, "substituted hydrocarbylene" refers to a hydrocarbylene that is substituted with one or more substituents, and the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to a hydrocarbylene in which at least one carbon atom has been replaced with a heteroatom. Unless otherwise specified, the terms "hydrocarbyl" and "hydrocarbylene" shall be interpreted to include substituted and / or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.

[0035] The term "heteroatom-containing," as in "heteroatom-containing hydrocarbyl group," refers to a hydrocarbon or hydrocarbyl molecule fragment in which one or more carbon atoms have been replaced with an atom other than carbon, such as nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl" refers to an alkyl substituent containing a heteroatom, the term "heterocyclic" refers to a cyclic substituent containing a heteroatom, the terms "heteroaryl" and "heteroaromatic" refer to "aryl" and "aromatic" substituents, respectively, containing a heteroatom, and so forth. Note that a "heterocyclic" group or compound may or may not be aromatic, and further, a "heterocycle" may be monocyclic, bicyclic, or polycyclic, as described above for the term "aryl." Examples of heteroalkyl groups include, but are not limited to, alkoxyaryl, alkylsulfanyl-substituted alkyl, and N-alkylated aminoalkyl. Examples of heteroaryl substituents include, but are not limited to, pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, and the like; examples of heteroatom-containing alicyclic groups include, but are not limited to, pyrrolidino, morpholino, piperazino, piperidino, and the like.

[0036] The term "heterocyclic carbene" refers to a neutral electron-donating ligand comprising a carbene molecule, where the carbene carbon atom is contained in a ring structure that also contains at least one heteroatom. Examples of heterocyclic carbenes include "N-heterocyclic carbenes," in which the heteroatom is nitrogen, and "P-heterocyclic carbenes," in which the heteroatom is phosphorus.

[0037] "Substituted," as in "substituted hydrocarbyl," "substituted alkyl," and "substituted aryl," means that at least one hydrogen atom bonded to a carbon atom (or other atom) in a hydrocarbyl, alkyl, aryl, or other moiety has been replaced with one or more non-hydrogen substituents. Examples of substituents include, but are not limited to, functional groups referred to herein as "Fn," e.g., halo, hydroxyl, sulfhydryl, C1-C 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 24 Aryloxy, C6-C 24 Aralkyloxy, C6-C 24 Alkyloxy, acyl (C2-C 24 Alkylcarbonyl (-CO-alkyl) and C6-C 24 arylcarbonyl (-CO-aryl), acyloxy (C2-C 24 Alkylcarbonyloxy (-O-CO-alkyl) and C6-C 24 Arylcarbonyloxy (-O-CO-aryl, -O-acyl), C2-C 24 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C 24 Aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X, where X is halo), C-C 24 Alkylcarbonate (-O-(CO)-O-alkyl), C6-C 24 Arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (-COO - ), carbamoyl (-(CO)-NH2), mono-(C1-C 24 Alkyl) substituted carbamoyl (-(CO)-NH(C1-C 24 alkyl), di-(C1-C 24 Alkyl) substituted carbamoyl (-(CO)-N(C1-C 24 alkyl)2), mono-(C1-C 24 Haloalkyl) substituted carbamoyl (-(CO)-NH(C1-C 24haloalkyl), di-(C1-C 24 Haloalkyl) substituted carbamoyl (-(CO)-N(C1-C 24 haloalkyl)2), mono-(C5-C 24 aryl) substituted carbamoyl (-(CO)-NH-aryl), di-(C5-C 24 Aryl) substituted carbamoyl (-(CO)-N(C5-C 24 aryl)2), di-N-(C1-C 24 alkyl), N-(C5-C 24 Aryl) substituted carbamoyl (-(CO)-N(C1-C 24 Alkyl) (C5-C 24 aryl), thiocarbamoyl (-(CS)-NH), mono-(C1-C 24 Alkyl) substituted thiocarbamoyl (-(CS)-NH(C1-C 24 alkyl), di-(C1-C 24 Alkyl) substituted thiocarbamoyl (-(CS)-N(C1-C 24 Alkyl)2), mono-(C5-C 24 aryl) substituted thiocarbamoyl (-(CS)-NH-aryl), di-(C5-C 24 Aryl) substituted thiocarbamoyl (-(CS)-N(C5-C 24 aryl)2), di-N-(C1-C 24 alkyl), N-(C5-C 24 Aryl) substituted thiocarbamoyl (-(CS)-N(C1-C 24 Alkyl) (C5-C 24 aryl), carbamide (-NH-(CO)-NH2), cyano (-C≡N), cyanato (-OC≡N), thiocyanato (-SC≡N), isocyanate (-N=C=O), thioisocyanate (-N=C=S), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono-(C1-C 24 Alkyl) substituted amino (-NH(C1-C 24 alkyl), di-(C1-C 24 Alkyl) substituted amino (-N(C1-C 24 Alkyl)2), mono-(C5-C 24 Aryl) substituted amino (-NH(C5-C24 aryl), di-(C5-C 24 Aryl) substituted amino (-N(C5-C 24 Aryl)2), C2-C 24 Alkylamide (-NH-(CO)-alkyl), C6-C 24 Arylamide (—NH—(CO)-aryl), imino (—CR═NH, where R is, but is not limited to, hydrogen, C1-C 24 Alkyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 (including aralkyl, etc.), C2-C 20 Alkylimino (-CR=N(alkyl), where R is an alkyl group including, but not limited to, hydrogen, C1-C 24 Alkyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 aralkyl, etc.), arylimino (-CR=N(aryl), where R is, but is not limited to, hydrogen, C1-C 20 Alkyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (-SO2-O - ), C1~C 24 Alkylsulfanyl (-S-alkyl, also known as "alkylthio"), C5-C 24 Arylsulfanyl (-S-aryl, also known as "arylthio"), C1-C 24 Alkylsulfinyl (-(SO)-alkyl), C5-C 24 Arylsulfinyl (-(SO)-aryl), C1-C 24 Alkylsulfonyl (-SO2-alkyl), C1-C 24 Monoalkylaminosulfonyl (-SO2-N(H) alkyl), C1-C 24 Dialkylaminosulfonyl (-SO2-N(alkyl)2), C5-C 24Arylsulfonyl (-SO2-aryl), boryl (-BH2), borono (-B(OH)2), boronato (-B(OR)2, where R includes, but is not limited to, alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O - )2), phosphinato (-P(O)(O - )), phospho (-PO2) and phosphino (-PH2); and hydrocarbyl moieties C1-C 24 Alkyl (preferably C1-C 12 alkyl, more preferably C1 to C6 alkyl), C2 to C 24 Alkenyl (preferably C2-C 12 alkenyl, more preferably C2-C6 alkenyl), C2-C 24 Alkynyl (preferably C2-C 12 alkynyl, more preferably C2-C6 alkynyl), C5-C 24 Aryl (preferably C5-C 14 Aryl), C6-C 24 Alkaryl (preferably C6-C 16 Alkaryl) and C6-C 24 Aralkyl (preferably C6-C 16 aralkyl).

[0038] "Functionalized," as in "functionalized hydrocarbyl," "functionalized alkyl," "functionalized olefin," and "functionalized cyclic olefin," means that at least one hydrogen atom bonded to a carbon atom (or other atom) in a hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety has been replaced with one or more functional groups, such as those described herein above. The term "functional group" is meant to include any functional species suitable for use as described herein. In particular, as used herein, a functional group will necessarily have the ability to react with or bond to a corresponding functional group on a substrate surface.

[0039] In addition, the aforementioned functional groups may, where a particular group permits, be further substituted with one or more additional functional groups or one or more hydrocarbyl moieties, such as those specifically listed above. Similarly, the aforementioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties, such as those detailed above. Similarly, the aforementioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties, as described above.

[0040] The term "ROMP" refers to ring-opening metathesis polymerization.

[0041] The term "substrate material" as used herein is intended to generally refer to any material with which the resin composition of the present invention may come into contact, be applied, or have a substrate material incorporated therein. Such materials include, but are not limited to, glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, and polyolefin or other polymer fibers or fabrics, such as filaments, fibers, rovings, mats, woven fabrics, fabrics, knitted materials, and other known structures. Other suitable substrate materials include metal density modifiers, particulate density modifiers (e.g., microspheres, glass microspheres, ceramic microspheres, microballoons, cenospheres), and macroparticle density modifiers (e.g., glass or ceramic beads). The resin composition may contain one substrate material or a mixture of various substrate materials.

[0042] "Optionally" or "optionally" means that the circumstance described below may or may not occur, and thus the description includes cases where the circumstance occurs and cases where the circumstance does not occur. For example, the phrase "optionally substituted" means that substituents other than hydrogen may or may not be present on a given atom, and thus the description includes structures where substituents other than hydrogen are present and structures where substituents other than hydrogen are not present.

[0043] The term "exotherm time" is defined herein as the amount of time (i.e., the difference in time) elapsed between the time when the cyclic olefin first contacts the catalyst to form the ROMP composition and the time when the temperature of the ROMP composition first increases by more than 1°C / sec. The terms "time to exotherm" and "exotherm time" have the same meaning and are used interchangeably herein. The peak exotherm temperature is the maximum temperature reached by the ROMP composition during a polymerization cycle. The exotherm peak time is defined as the amount of time (i.e., the difference in time) elapsed between the time when the cyclic olefin first contacts the catalyst to form the ROMP composition and the time when the ROMP composition reaches the peak exotherm temperature. Alternatively, the exotherm time can be defined as the amount of time (i.e., the difference in time) elapsed between the time when the cyclic olefin first contacts the catalyst to form the ROMP composition and the time when a propagating interface of the ROMP composition is first visually observed as the ROMP composition transitions from a liquid state (e.g., a monomer state) or gel state to a cured polymer state. The observation of a propagating interface is typically accompanied by a temperature increase, often a significant temperature increase, of the ROMP composition. The temperature rise can be measured by a thermocouple or similar temperature measuring and / or recording device.

[0044] Metal Carbene Olefin Metathesis Catalysts In one embodiment, the metal carbene olefin metathesis catalyst of the present invention comprises a Group 8 transition metal complex having the structure of formula (I): [ka] During the ceremony, L 1 is a carbene ligand having the structure of formula (II): [ka] M is a Group 8 transition metal, specifically ruthenium or osmium, more specifically ruthenium; X and Y are independently CH, C, N, O, S or P, preferably both X and Y are N; Q 1 , Q2 , Q 3 and Q 4 is independently a linker, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, e.g., substituted alkylene and / or heteroatom-containing alkylene) or —(CO)—; Q 1 , Q 2 , Q 3 and Q 4 two or more substituents on adjacent atoms in may be joined to form an additional cyclic group; p and q are independently 0, 1, or 2; w, x, y and z are independently 0 or 1, preferably w, x, y and z are 0; R 3 , R 3A , R 4 and R 4A are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl; L 2 is a phosphinite or phosphonite ligand, X 1 and X 2 are independently an anionic ligand and are bonded to M in a trans or cis configuration; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), however, When X is O or S, p is 0; When X is N, CH or P, p is 1; When X is C, p is 2; when Y is O or S, q is 0; when Y is N, CH or P, q is 1; When Y is C, q is 2; and only one of X or Y is C or CH; The catalyst of formula (I) is provided that it does not have the following structure: [ka]

[0045] In one embodiment, L 2 is expressed as equation (1): [ka] (R 3p )(R 2p )POR 1p (In the formula, R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3 to C8 cycloalkyl).

[0046] In another embodiment, L 2 is expressed as equation (2): [ka] R 10p P(OR 9p )(OR 8p )(wherein, R 8p , R 9p , R 10p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10alkyl, or substituted or unsubstituted C3 to C8 cycloalkyl).

[0047] In a further embodiment, the metal carbene olefin metathesis catalyst of the present invention comprises a Group 8 transition metal complex having the structure of formula (III): [ka] During the ceremony, M is a Group 8 transition metal, specifically ruthenium or osmium, more specifically ruthenium; X and Y are independently C, CH, N, O, S or P, preferably both X and Y are N; Q 1 , Q 2 , Q 3 and Q 4 is independently a linker, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, e.g., substituted alkylene and / or heteroatom-containing alkylene) or —(CO)—; Q 1 , Q 2 , Q 3 and Q 4 two or more substituents on adjacent atoms in may be joined to form an additional cyclic group; p and q are independently 0, 1, or 2; w, x, y and z are independently 0 or 1, preferably w, x, y and z are 0; R 3 , R 3A , R 4 and R 4A are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl; L 2 is a phosphinite or phosphonite ligand, X 1 and X 2 are independently an anionic ligand and are bonded to M in a trans or cis configuration; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), provided that: When X is O or S, p is 0; When X is N or P, p is 1; When X is C, p is 2; when Y is O or S, q is 0; when Y is N, CH or P, q is 1; When Y is C, q is 2; and only one of X or Y is C or CH; The catalyst of formula (III) is provided that it does not have the following structure: [ka]

[0048] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (IIIa): [ka] In the formula, M, L 2 , p, q, m, w, x, y, z, R 1 , R 2 , R 3 , R 4 , X, Y, R 3A , R 4A , X 1 , X 2 , Q 1 , Q 2 , Q 3 , Q4 is as defined above for the complex having the structure of formula (III), wherein the complex is a positional isomer and X 1 and X 2 is attached to M in a trans configuration, with the proviso that the catalyst of formula (IIIa) is not of the structure: [ka]

[0049] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (IIIb): [ka] In the formula, M, L 2 , p, q, m, w, x, y, z, R 1 , R 2 , R 3 , R 4 , X, Y, R 3A , R 4A , X 1 , X 2 , Q 1 , Q 2 , Q 3 , Q 4 is as defined above for the complex having the structure of formula (III), wherein the complex is a positional isomer and X 1 and X 2 is attached to M in a cis configuration, with the proviso that the catalyst of formula (IIIb) is not of the structure: [ka]

[0050] Among the carbene ligands having the structure of formula (II), R 3A and R 4A are linked to form a cyclic group, and at least one of X or Y is nitrogen, or Q 3 or Q 4A particular class, in which at least one of the groups is a heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene, and at least one heteroatom is nitrogen, are commonly referred to as N-heterocyclic carbene (NHC) ligands.

[0051] Preferably, R 3A and R 4A are bonded to form a cyclic group, which allows the carbene ligand L 1 has the structure of formula (IV): [ka] In the formula, R 3 and R 4 At least one of or R 3 and R 4 and (b) are alicyclic or aromatic groups having from 1 to about 5 rings, and optionally contain one or more heteroatoms and / or substituents. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene linkers, heteroatom-containing hydrocarbylene linkers, and substituted heteroatom-containing hydrocarbylene linkers. Two or more substituents on adjacent atoms in Q may also be joined to form additional ring structures, which may also be substituted to provide fused polycyclic structures of from 2 to about 5 ring groups. Q is often, but not necessarily, a two-atom or three-atom bond.

[0052] R 3 and R 4 When R are aromatic, they typically, but not necessarily, consist of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, etc. In one preferred embodiment, R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 and phenyl substituted with up to three substituents selected from alkaryl or halide. Preferably, any substituents present are hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide. 3 and R 4 is 2,4,6-trimethylphenyl (i.e., mesityl or Mes as defined herein). 3 and R 4 is 2,6-diisopropylphenyl (i.e., DIPP or DiPP as defined herein).

[0053] Therefore, L 1 Examples of N-heterocyclic carbene (NHC) and acyclic diaminocarbene ligands suitable as include, but are not limited to, the following: wherein DIPP or DiPP is 2,6-diisopropylphenyl and Mes is 2,4,6-trimethylphenyl. [ka] L 1 Further examples of N-heterocyclic carbene (NHC) ligands suitable as include 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene) (ie, sIMes). [ka]

[0054] L 1Further examples of N-heterocyclic carbene (NHC) ligands suitable as include 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) (ie, IMes). [ka]

[0055] Therefore, L 1 Further examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as include, but are not limited to: [ka] In the formula, R W1 , R W2 , R W3 , R W4 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl; R W3 and R W4 One or both of L may be independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups. 1 Further examples of suitable N-heterocyclic carbene (NHC) ligands are further described in U.S. Patent Nos. 7,378,528, 7,652,145, 7,294,717, 6,787,620, 6,635,768, and 6,552,139, the contents of each of which are incorporated herein by reference. Additionally, the thermally activated N-heterocyclic carbene precursors disclosed in U.S. Patent No. 6,838,489, the contents of which are incorporated herein by reference, can also be used with the present invention.

[0056] R 3 and R 4 When R are aromatic, they typically, but not necessarily, consist of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, etc. In one preferred embodiment, R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 and phenyl substituted with up to three substituents selected from alkaryl or halide. Preferably, any substituents present are hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide. 3 and R 4 is 2,4,6-trimethylphenyl, and as another example, R 3 and R 4 is 2,6-diisopropylphenyl.

[0057] In another embodiment, L 2 is expressed as equation (1): (R 3p )(R 2p )POR 1p (In the formula, R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3 to C8 cycloalkyl).

[0058] In one example, R 1pis selected from methyl (-CH3), ethyl (-CH2CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2CH2CH2CH3), sec-butyl (-CH(CH3)(CH2CH3), tert-butyl (-C(CH3)3), 4-methoxyphenyl (-(C6H4)(para-OCH3), benzyl (-CH2C6H5), or phenyl (-C6H5); R 2p and R 3p are each phenyl (-C6H5). In another example, R 1p is selected from methyl (-CH), ethyl (-CHCH), isopropyl (-CH(CH)), 4-methoxyphenyl (-(CH)para-OCH), or phenyl (-CH); R 2p and R 3p are each phenyl (-C6H5). In another example, R 1p is selected from methyl (-CH), ethyl (-CHCH), isopropyl (-CH(CH)), or phenyl (-CH); R 2p and R 3p are each phenyl (-C6H5). In another example, R 1p is selected from methyl (-CH), isopropyl (-CH(CH)), or phenyl (-C6H5), and R 2p and R 3p are each phenyl (-C6H5). In another example, R 1p is selected from methyl (-CH), ethyl (-CHCH), or isopropyl (-CH(CH)); R 2p and R 3p are each phenyl (-C6H5). In another example, R 1p is phenyl (-C6H5), and R 2p and R 3p are phenyl (-C6H5), respectively.

[0059] In another embodiment, L 2 is expressed by the formula (2):R 10p P(OR 9p )(OR 8p )(wherein, R 8p , R9p , R 10p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3 to C8 cycloalkyl).

[0060] In one example, R 8p and R 9p are each independently selected from methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; R 10p is phenyl. In another example, R 8p and R 9p are methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl, respectively, and R 10p is phenyl. In another example, R 8p and R 9p are each methyl, ethyl, isopropyl, or phenyl, and R 10p is phenyl. In another example, R 8p and R 9p are methyl, isopropyl, or phenyl, respectively, and R 10p is phenyl. In another example, R 8p and R 9p are methyl or isopropyl, respectively, and R 10p is phenyl. In another example, R 8p and R 9p are phenyl, and R 10p is phenyl.

[0061] In certain embodiments, R 1 and R 2 is hydrogen, hydrocarbyl (e.g., C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C5-C 24 Aryl, C6-C24 Alkaryl, C6-C 24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., C1-C containing heteroatoms), 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 aralkyl, etc.) and substituted heteroatom-containing hydrocarbyls (e.g., substituted C-C containing heteroatoms). 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C5-C 24 Aryl, C6-C 24 Alkaryl, C6-C 24 aralkyl, etc.) and functional groups. R 1 and R 2 may also be linked to form a cyclic group, which may be aliphatic or aromatic and may contain substituents and / or heteroatoms. Generally, such cyclic groups contain 4 to 12 ring atoms, preferably 5, 6, 7, or 8 ring atoms.

[0062] In preferred catalysts, R 1 is hydrogen and R 2 is C1~C 20 Alkyl, C2-C 20 Alkenyl and C5-C 24 aryl, more preferably C1-C6 alkyl, C2-C6 alkenyl and C5-C 14 Even more preferably, R is selected from aryl. 2is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl, and functional groups Fn as defined herein above. Most preferably, R 2 is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. 2 is phenyl or -CH=C(CH3)2. 1 and R 2 may be taken together to form an indenylidene moiety, preferably phenylindenylidene.

[0063] In certain embodiments, X 1 and X 2 are anionic ligands and may be the same or different or may be joined together to form a cyclic group, typically, but not necessarily, a 5- to 8-membered ring. In preferred embodiments, X 1 and X 2 are each independently hydrogen, halide, or one of the following groups: C1 to C 20 Alkyl, C5-C 24 Aryl, C1-C 20 Alkoxy, C5-C 24 Aryloxy, C2-C 20 Alkoxycarbonyl, C6-C 24 Aryloxycarbonyl, C2-C 24 Acyl, C2-C 24 Acyloxy, C1-C 20 Alkyl sulfonates, C5-C 24 Arylsulfonates, C1-C 20 Alkylsulfanyl, C5-C 24 Arylsulfanyl, C1-C 20 Alkyl sulfinyl, NO3, -N=C=O, -N=C=S or C5-C 24 arylsulfinyl. 1 and X 2 is C1~C 12Alkyl, C1-C 12 Alkoxy, C5-C 24 It may be substituted with one or more moieties selected from aryl and halide, and these one or more moieties may be further substituted with one or more groups selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl, excluding halide. 1 and X 2 is halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, aryl, or C1-C6 alkylsulfonyl. 1 and X 2 are respectively halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate or trifluoromethanesulfonate. 1 and X 2 are chlorides, respectively.

[0064] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V): [ka] During the ceremony, Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans or cis configuration; L 2 is a phosphinite or phosphonite ligand, m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (V) is not of the following structure: [ka]

[0065] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V), wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following may comprise one or more of the linkers; 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; L 2 is a phosphinite or phosphonite ligand, m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (V) is not of the following structure: [ka]

[0066] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V): m is 0, Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl; X 1 and X 2 is Cl and is bonded to Ru in a trans configuration, L 2 is a phosphinite ligand, R 1 is hydrogen and R 2 is phenyl, vinyl optionally substituted with one or more moieties selected from C1-C6 alkyl or C1-C6 alkoxy, or R 1 and R 2 may be linked together to form a phenylindenylidene, and the catalyst of formula (V) is not of the structure [ka]

[0067] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V): m is 0, Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl; X 1 and X 2 is Cl and is bonded to Ru in a trans configuration, L 2 is a phosphonite ligand, R 1 is hydrogen and R 2 is phenyl, vinyl optionally substituted with one or more moieties selected from C1-C6 alkyl or C1-C6 alkoxy, or R 1 and R 2 may be linked together to form a phenylindenylidene.

[0068] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V): Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are each phenyl substituted with up to three substituents selected from methyl or isopropyl; X 1 and X2 is Cl and is bonded to Ru in a trans configuration, L 2 is a phosphinite or phosphonite ligand, m is 0, R 1 is hydrogen and R 2 is phenyl, phenyl-o-isopropyl-CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may be linked together to form a phenylindenylidene; The catalyst of formula (V) is not of the following structure: [ka]

[0069] In another embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (V), wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following may comprise one or more of the linkers; 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; L 2 is a phosphinite or phosphonite ligand, m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (V) is not of the following structure: [ka]

[0070] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (Va): [ka] During the ceremony, Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; L 2 is a phosphinite or phosphonite ligand, m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), provided that: The catalyst of formula (Va) is provided that it does not have the following structure: [ka]

[0071] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (Va): In the formula, L 2 , R 1 , R 2 , X 1 and X 2 are as defined above for the complex having the structure of formula (V), and Q, R 3 and R 4 is as defined above for N-heterocyclic carbene (NHC) ligands having the structure of formula (IV) or formula (V), wherein the complexes are positional isomers, and wherein X 1 and X 2 is attached to Ru in a trans configuration, with the proviso that The catalyst of formula (Va) is provided that it does not have the following structure: [ka]

[0072] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (Vb): [ka] During the ceremony, Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; L 2 is a phosphinite or phosphonite ligand, m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), provided that: The catalyst of formula (Vb) is provided that it does not have the following structure: [ka]

[0073] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (Vb): In the formula, L 2 , R 1 , R 2 , X 1 and X 2are as defined above for the complex having the structure of formula (V), and Q, R 3 and R 4 is as defined above for N-heterocyclic carbene (NHC) ligands having the structure of formula (IV) or formula (V), wherein the complexes are positional isomers, and wherein X 1 and X 2 is bound to Ru in a cis configuration, with the proviso that The catalyst of formula (Vb) is provided that it does not have the following structure: [ka]

[0074] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): [ka] Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans or cis configuration; R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (VI) is not of the following structure: [ka]

[0075] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and phenyl, where each phenyl is C1 to C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may together form an indenylidene moiety, preferably phenylindenylidene; The catalyst of formula (VI) is not of the following structure: [ka]

[0076] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R4 are identical and phenyl, where each phenyl is C1 to C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; R 1p , R 2p , R 3p are each independently methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may be taken together to form an indenylidene moiety, preferably a phenylindenylidene, and the catalyst of formula (VI) is not of the structure [ka]

[0077] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and are phenyl, where each phenyl is C1-C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2are independently chloride and are attached to Ru in a trans configuration; R 1p is methyl, ethyl, isopropyl or phenyl, R 2p is phenyl, R 3p is phenyl, m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may be taken together to form an indenylidene moiety, preferably a phenylindenylidene, and the catalyst of formula (VI) is not of the structure [ka]

[0078] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and phenyl, where each phenyl is C1 to C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may together form an indenylidene moiety, preferably phenylindenylidene; The catalyst of formula (VI) is not of the following structure: [ka]

[0079] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and are phenyl, and each phenyl is C1 to C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; R 1p , R 2p , R 3p are each independently methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; m is 0 or 1; R 1 is hydrogen and R 2is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may together form an indenylidene moiety, preferably phenylindenylidene; The catalyst of formula (VI) is not of the following structure: [ka]

[0080] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VI): wherein Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and phenyl, where each phenyl is C1 to C 20 substituted with up to three substituents selected from alkyl; X 1 and X 2 is a chloride and is bonded to Ru in a cis configuration, R 1p is methyl, isopropyl or phenyl, R 2p is phenyl, R 3p is phenyl, m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, -CH=CH(tert-butyl) or -CH=C(CH3)2, or R 1 and R 2 may together form an indenylidene moiety, preferably phenylindenylidene; The catalyst of formula (VI) is not of the following structure: [ka]

[0081] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIa): [ka] wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (VIa) is not of the following structure: [ka]

[0082] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIa): In the formula, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , m, R 1p , R 2p , R 3p and Q are as defined above for the complex having the structure of formula (VI), where the complex is a positional isomer, and X 1 and X 2 is attached to Ru in a trans configuration, with the proviso that the catalyst of formula (VIa) is not of the structure [ka]

[0083] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIb): [ka] wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; R 1p , R 2p , R 3p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring), The catalyst of formula (VIb) is not of the following structure: [ka]

[0084] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIb): In the formula, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , m, R 1p , R 2p , R 3p and Q are as defined above for the complex having the structure of formula (VI), where the complex is a positional isomer, and X 1 and X 2 is attached to Ru in a cis configuration, with the proviso that the catalyst of formula (VIb) is not of the structure [ka]

[0085] In certain embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VII): [ka] wherein Q is the structure -CR11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans or cis configuration; R 8p , R 9p , R 10p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring).

[0086] In other embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VII), wherein: Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are the same, C1 to C 20 phenyl substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; R 8p , R 9p , R 10p are each independently methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, 2-isopropoxyphenyl or -CH=C(CH3)2, or R 1 and R 2 may be taken together to form an indenylidene moiety, preferably phenylindenylidene.

[0087] In other embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VII), wherein: Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are the same, C1 to C 20 phenyl substituted with up to three substituents selected from alkyl; X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; R 8p , R 9p , R 10p are each independently methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 4-methoxyphenyl, benzyl, or phenyl; m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, 2-isopropoxyphenyl or -CH=C(CH3)2, or R 1 and R 2 may be taken together to form an indenylidene moiety, preferably phenylindenylidene.

[0088] In other embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VII), wherein: Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and mesityl, X1 and X 2 is a chloride and is attached to Ru in a trans configuration, R 8p is methyl, R 9p is methyl, R 10p is phenyl, m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, 2-isopropoxyphenyl or -CH=C(CH3)2, or R 1 and R 2 may be taken together to form an indenylidene moiety, preferably phenylindenylidene.

[0089] In other embodiments, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VII), wherein: Q is the structure -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, R 3 and R 4 are identical and mesityl, X 1 and X 2 is a chloride and is bonded to Ru in a cis configuration, R 8p is methyl, R 9p is methyl, R 10p is phenyl, m is 0 or 1; R 1 is hydrogen and R 2 is phenyl, 2-isopropoxyphenyl or -CH=C(CH3)2, or R 1 and R 2may be taken together to form an indenylidene moiety, preferably phenylindenylidene.

[0090] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIIa): [ka] wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a trans configuration; R 8p , R 9p , R 10p are each independently a substituted or unsubstituted C to C 10Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring).

[0091] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIIa): In the formula, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , m, R 8p , R 9p , R 10p and Q are as defined above for the complex having the structure of formula (VII), wherein the complex is a positional isomer, 1 and X 2 is bound to Ru in a trans configuration.

[0092] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIIb): [ka] wherein Q is the structure -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 -, preferably -CR11 R 12 -CR 13 R 14 - a two-atom bond, wherein R 11 , R 12 , R 13 and R 14 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group, preferably independently hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 heteroalkyl, phenyl, or substituted phenyl; or R 11 , R 12 , R 13 and R 14 Any two of these may be bonded together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., C4-C 12 The ring structure may form an alicyclic group or a C5 or C6 aryl group, and the ring structure may itself be substituted, for example with linked or fused alicyclic or aromatic groups or other substituents, or may be substituted by R 11 , R 12 , R 13 and R 14 any one or more of the following comprises one or more of the linkers; R 3 and R 4 can be unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24They may be phenyl substituted with one or more substituents such as alkaryl or halide, or they may be aromatic, typically, but not necessarily, consisting of one or two aromatic rings which may be substituted or unsubstituted, e.g., R 3 and R 4 can be phenyl, substituted phenyl, biphenyl, or substituted biphenyl, and preferably R 3 and R 4 are the same and each is unsubstituted phenyl or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 Heteroaryl, C6-C 24 Aralkyl, C6-C 24 Phenyl substituted with up to three substituents selected from alkaryl and halide, the preferred substituents present being hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 aryl or halide, X 1 and X 2 are independently halogen and are bonded to Ru in a cis configuration; R 8p , R 9p , R 10p are each independently a substituted or unsubstituted C to C 10 Aryl or substituted or unsubstituted C1-C 10 alkyl, or substituted or unsubstituted C3-C8 cycloalkyl; m is 0, 1 or 2; R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2are bonded together to form a ring (e.g., C4 to C 10 ring or C5-C6 ring), which may be substituted or unsubstituted, saturated or unsaturated, and may be fused or linked to form further rings (e.g., C4-C 10 ring or C5-C6 ring).

[0093] In one embodiment, the metal carbene olefin metathesis catalyst of the present invention is represented by the structure of formula (VIIb): In the formula, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , m, R 8p , R 9p , R 10p and Q are as defined above for the complex having the structure of formula (VII), wherein the complex is a positional isomer, 1 and X 2 is bound to Ru in a cis configuration.

[0094] Numerous embodiments of the metal carbene olefin metathesis catalysts of the present invention are detailed below.

[0095] Non-limiting examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) include the following, some of which, for convenience, are identified throughout this disclosure by reference to molecular weight: [ka]

[0096] Non-limiting examples of metal carbene olefin metathesis catalysts having the structure of formula (VII) include the following, some of which, for convenience, are identified throughout this disclosure by reference to molecular weight: [ka]

[0097] Further examples of metal carbene olefin metathesis catalysts having the structure of formula (VI) disclosed herein include the following: trans-RuCl(sIMes)(CHCHOi-Pr)(PhP(OMe))(trans-C843), trans-RuCl(sIMes)(benzylidene)(P(OPh))(trans-C847), trans-RuCl(sIMes)(phenylindenylidene)(P(OMe))(trans-C885), trans-RuCl(sIMes)(phenylindenylidene)(P(OPh))(trans-C947), trans-RuCl(sIMes)(phenylindenylidene)(P(OP-C6H4 trans-RuCl(sIMes)(phenylindenylidene) (PhP(OiPr)) (trans-C913), trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OiPr)) (trans-C791), trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OMe)) (trans-C763), trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OEt)) (trans-C777), trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OPh)) (trans-C825).

[0098] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: trans-RuCl(sIMes)(CHCHO-Pr)(PhP(OMe))(trans-C).

[0099] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: trans-RuCl(sIMes)(benzylidene)(PhP(OPh))(trans-C847).

[0100] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: trans-RuCl(sIMes)(phenylindenylidene) (PhP(OMe)) (trans-C885), trans-RuCl(sIMes)(phenylindenylidene) (PhP(OPh)) (trans-C947), trans-RuCl(sIMes)(phenylindenylidene) (PhP(Op-C6H4OMe)) (trans-C977), trans-RuCl(sIMes)(phenylindenylidene) (PhP(OiPr)) (trans-C913), trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OPh)) (trans-C825).

[0101] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: trans-RuCl(sIMes)(3-methyl-2-butenylidene)(PhP(OiPr))(trans-C791), trans-RuCl(sIMes)(3-methyl-2-butenylidene)(PhP(OMe))(trans-C763), trans-RuCl(sIMes)(3-methyl-2-butenylidene)(PhP(OEt))(trans-C777).

[0102] Further examples of metal carbene olefin metathesis catalysts having the structure of formula (VI) disclosed herein include the following: cis-RuCl(sIMes)(CHCHOi-Pr)(PhP(OMe))(cis-C43), cis-RuCl(sIMes)(phenylindenylidene)(PhP(OMe))(cis-C885), cis-RuCl(sIMes)(phenylindenylidene)(PhP(OPh))(cis-C947), cis-RuCl(sIMes)(phenylindenylidene)(Ph cis-RuCl(sIMes)(phenylindenylidene)(PhP(Oi-Pr))(cis-C913), cis-RuCl(sIMes)(phenylindenylidene)(PhP(OMe))(cis-C834), cis-RuCl(sIMes)(t-butylvinylidene)(PhP(OMe))(cis-C777v), cis-RuCl(sIMes)(t-butylvinylidene)(PhP(Oi-Pr))(cis-C805v).

[0103] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: cis-RuCl(sIMes)(CHCHO-Pr)(PhP(OMe))(cis-C).

[0104] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: cis-RuCl(sIMes)(phenylindenylidene) (PhP(OMe))(cis-C88S), cis-RuCl(sIMes)(phenylindenylidene) (PhP(OPh))(cis-C947), cis-RuCl(sIMes)(phenylindenylidene) (PhP(Op-C6H4OMe))(cis-C977), cis-RuCl(sIMes)(phenylindenylidene) (PhP(Oi-Pr))(cis-C913).

[0105] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VI) disclosed herein include the following: cis-RuCl(sIMes)(t-butylvinylidene)(PhP(OMe))(cis-C777v), cis-RuCl(sIMes)(t-butylvinylidene)(PhP(Oi-Pr))(cis-C805v).

[0106] Further examples of metal carbene olefin metathesis catalysts having the structure of formula (VII) disclosed herein include the following: trans-RuCl(sIMes)(benzylidene)(PhP(OMe))(trans-C139), trans-RuCl(sIMes)(phenylindenylidene)(PhP(OMe))(trans-C834), trans-RuCl(sIMes)(3-methyl-2 ... -butenylidene)(PhP(OMe)2)(trans-C717), cis-RuCl2(sIMes)(benzylidene)(PhP(OMe)2)(cis-739), cis-RuCl2(sIMes)(CHC6H4Oi-Pr)(PhP(OMe)2)(cis-C797), cis-RuCl2(sIMes)(phenylindenylidene)(PhP(OMe)2)(cis-C834).

[0107] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VII) disclosed herein include the following: trans-RuCl(sIMes)(benzylidene)(PhP(OMe))(trans-C139), trans-RuCl(sIMes)(phenylindenylidene)(PhP(OMe))(trans-C834), trans-RuCl(sIMes)(3-methyl-2-butenylidene)(PhP(OMe))(trans-C717), cis-RuCl(sIMes)(benzylidene)(PhP(OMe)), trans-RuCl(sIMes)(phenylindenylidene)(PhP(OPh))(trans-C963).

[0108] Further examples of metal carbene olefin metathesis catalysts having the structure of Formula (VII) disclosed herein include the following: (cis-739), cis-RuCl(sIMes)(CHCHO-Pr)(PhP(OMe))(cis-C797), cis-RuCl(sIMes)(phenylindenylidene)(PhP(OMe))(cis-C834).

[0109] The present invention also relates to a process for preparing the above-described metal carbene olefin metathesis catalyst. The metal carbene olefin metathesis catalyst of the present invention can be prepared in a manner similar to conventional methods understood by those skilled in the art of organic synthetic chemistry. For example, the synthetic schemes 2 and 3 shown below illustrate how the compounds of the present invention can be produced. [ka]

[0110] L 2 Metal carbene olefin metathesis catalysts of formula (III) where R is the phosphinite ligand have been prepared according to general scheme 3. Generally, 3 , R 4 , Q, X 1 , X 2 , m, R 1 and R 2 is as defined in the case of formula (III) and L is a neutral electron donor ligand), reacting with an excess of phosphinite provides the corresponding metal carbene olefin metathesis catalyst represented by formula (VI). [ka]

[0111] L 2Metal carbene olefin metathesis catalysts of formula (III), where is the phosphonite ligand, were prepared according to general scheme 3. Generally, reaction of a metal carbene olefin metathesis catalyst as described above, represented by formula (IIIS), with an excess of a phosphonite ester affords the corresponding metal carbene olefin metathesis catalyst represented by formula (III).

[0112] In one embodiment, the reactions of Synthetic Scheme 2 or 3 are carried out in dichloromethane or toluene under degassed N at room temperature or elevated temperature. Upon completion of the reaction, the mixture is cooled to room temperature, the solvent is removed under high vacuum, and the residue is purified on a silica gel column and then recrystallized to afford the novel metal carbene olefin metathesis catalyst.

[0113] At this stage, one skilled in the art will appreciate that many additional compounds falling within the scope of this invention can be prepared by practicing various general chemical reactions. Details of certain specific chemical transformations are provided in the Examples.

[0114] Metal carbene olefin metathesis catalysts can be used in olefin metathesis reactions according to techniques known in the art. For example, metal carbene olefin metathesis catalysts are typically added to resin compositions as a solid, solution, or suspension. When the metal carbene olefin metathesis catalyst is added to a resin composition as a suspension, the metal carbene olefin metathesis catalyst is suspended in a dispersing carrier, such as mineral oil, paraffin oil, soybean oil, triisopropylbenzene, or any hydrophobic liquid that has a high enough viscosity to allow effective dispersion of the catalyst(s), is sufficiently inert, and has a high enough boiling point so as not to act as a low-boiling impurity in the olefin metathesis reaction. It will be understood that the amount of catalyst used in a reaction (i.e., the "catalyst loading") depends on various factors, such as the nature of the reactants and the reaction conditions employed. It will be understood, therefore, that the catalyst loading can be optimally and independently selected for each reaction. Generally, however, the catalyst will be present in an amount ranging from a lower limit of about 0.1 ppm, 1 ppm, or 5 ppm to an upper limit of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of olefin substrate (e.g., cyclic olefin).

[0115] The catalyst will generally be present in an amount ranging from a lower limit of about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to an upper limit of about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol%, relative to the olefin substrate (e.g., cyclic olefin).

[0116] When expressed as a molar ratio of monomer to catalyst ("monomer to catalyst ratio"), the catalyst addition will generally be present in an amount ranging from a lower limit of about 10,000,000:1, 1,000,000:1, 500,000:1, or 200,000:1 to an upper limit of about 100,000:1 60,000:1, 50,000:1, 45,000:1, 40,000:1, 30,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1. Cyclic olefins

[0117] The resin compositions that can be used in the invention disclosed herein include one or more cyclic olefins. Generally, any cyclic olefin suitable for the metathesis reactions disclosed herein can be used. Such cyclic olefins are mono-, di-, or higher polyunsaturated C5-C cyclic olefins that can be optionally substituted, optionally contain heteroatoms, and can be monocyclic, bicyclic, or polycyclic. 24 The cyclic olefin may be a hydrocarbon. The cyclic olefin may be any strained or unstrained cyclic olefin, provided that it can participate in the ROMP reaction either individually or as part of a ROMP cyclic olefin composition. While certain unstrained cyclic olefins, such as cyclohexene, are generally understood not to undergo the ROMP reaction themselves, under appropriate circumstances, such unstrained cyclic olefins may also be ROMP-active. For example, an unstrained cyclic olefin may be ROMP-active when present as a comonomer in a ROMP composition. Thus, as used herein and as understood by those skilled in the art, the term "unstrained cyclic olefin" is intended to refer to an unstrained cyclic olefin that can undergo the ROMP reaction under any conditions or in any ROMP composition, provided that the unstrained cyclic olefin is ROMP-active.

[0118] Cyclic olefins can generally be represented by the structure of formula (A): [ka] In the formula, J, RA1 and R A2 is as shown below. R A1 and R A2 is hydrogen, hydrocarbyl (e.g., C1-C 20 Alkyl, C5-C 20 Aryl, C5-C 30 Aralkyl or C5-C 30 alkaryl), substituted hydrocarbyl (e.g., substituted C1-C 20 Alkyl, C5-C 20 Aryl, C5-C 30 Aralkyl or C5-C 30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C 20 Heteroalkyl, C5-C 20 Heteroaryl, heteroatom-containing C5-C 30 Aralkyl or heteroatom-containing C5-C 30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C-C 20 Heteroalkyl, C5-C 20 Heteroaryl, heteroatom-containing C5-C 30 Aralkyl or heteroatom-containing C5-C 30 and in the case of a substituted hydrocarbyl or a substituted heteroatom-containing hydrocarbyl, the substituents are selected from the group consisting of phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C1-C 20 Alkylsulfanyl, C5-C 20 Arylsulfanyl, C1-C 20 Alkylsulfonyl, C5-C 20 Arylsulfonyl, C1-C 20 Alkylsulfinyl, C5-C 20 Arylsulfinyl, sulfonamide, amino, amido, imino, nitro, nitroso, hydroxyl, C1-C 20 Alkoxy, C5-C 20 Aryloxy, C2-C 20 Alkoxycarbonyl, C5-C 20 Aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C1-C20 R can be a functional group ("Fn") such as thioester, cyano, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal- or metalloid-containing group (where the metal can be, for example, Sn or Ge). A1 and R A2 may itself be one of the aforementioned groups, in which case the Fn moiety will be directly bonded to the olefinic carbon atom shown in the structure. However, in the latter case, the functional group generally will not be directly bonded to the olefinic carbon through a heteroatom containing one or more lone electron pairs (e.g., oxygen, sulfur, nitrogen, or phosphorus atoms) or through an electron-rich metal or metalloid (e.g., Ge, Sn, As, Sb, Se, Te, etc.). When such a functional group is present, it is usually bonded to the olefinic carbon through an intervening bond Z. * Therefore, R A1 and / or R A2 is the structure -(Z * ) n -Fn (wherein n is 1, Fn is a functional group, and Z * has a hydrocarbylene linking group, for example, an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage. J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene bond, and when J is a substituted hydrocarbylene or substituted heteroatom-containing hydrocarbylene, the substituents are one or more -(Z * ) n -Fn group (wherein n is 0 or 1, and Fn and Z *is as defined above). Additionally, two or more substituents attached to ring carbon atoms (or other atoms) in J may combine to form a bicyclic or polycyclic olefin. J generally contains in the range of about 5 to 14 ring atoms, typically in the range of 5 to 8 ring atoms, for monocyclic olefins, and for bicyclic and polycyclic olefins, each ring generally contains usually 4 to 8, typically 5 to 7 ring atoms.

[0119] The monounsaturated cyclic olefin encompassed by formula (A) can be represented by formula (B): [ka] wherein b is generally, but not necessarily, an integer ranging from 1 to 10, typically from 1 to 5; R A1 and R A2 is as defined above for formula (A), and R B1 , R B2 , R B3 , R B4 , R B5 and R B6 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z * ) n -Fn(where n, Z * and Fn are as defined above), and R B1 ~R B6 If any of the moieties is a substituted hydrocarbyl or a substituted heteroatom-containing hydrocarbyl, the substituents may be one or more -(Z * ) n -Fn groups. Thus, R B1 , R B2 , R B3 , R B4 , R B5 and R B6 is, for example, hydrogen, hydroxyl, C1-C 20 Alkyl, C5-C 20 Aryl, C1-C 20 Alkoxy, C5-C 20Aryloxy, C2-C 20 Alkoxycarbonyl, C5-C 20 It can be aryloxycarbonyl, amino, amido, nitro, etc. Furthermore, R B1 , R B2 , R B3 , R B4 , R B5 and R B6 If any of the parts are different from other R B1 , R B2 , R B3 , R B4 , R B5 and R B6 The linkage may be attached to either moiety to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, and the linkage may contain a heteroatom or a functional group, for example, but not limited to, an ether, ester, thioether, amino, alkylamino, imino, or an anhydride moiety. The alicyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono- or polyunsaturation, although monounsaturated cyclic groups are preferred. The ring, when substituted, contains mono- or polysubstitution, where the substituents are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn (wherein n is 0 or 1, and Z * and Fn are as defined above, and are independently selected from the functional group (Fn) as described above.

[0120] Examples of monounsaturated monocyclic olefins encompassed by formula (B) include, but are not limited to, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, as well as substituted forms thereof, such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxycyclopentene, 4-ethoxycyclopentene, cyclopent-3-enethiol, cyclopent-3-ene, 4-methylsulfanylcyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, and the like.

[0121] Monocyclic diene reactants encompassed by formula (A) can be generally represented by formula (C): [ka] where c and d are independently integers ranging from 1 to about 8, typically 2 to 4, preferably 2 (the reactant is cyclooctadiene), and R A1 and R A2 is as defined above for formula (A), and R C1 , R C2 , R C3 , R C4 , R C5 and R C6 is R B1 ~R B6 where R C3 and R C4is preferably a substituent other than hydrogen, in which case the second olefin moiety is tetrasubstituted. Examples of monocyclic diene reactants include, but are not limited to, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogs thereof. Triene reactants are similar to the diene formula (C) and generally contain at least one methylene bond between any two olefin segments.

[0122] The bicyclic and polycyclic olefins encompassed by formula (A) can be generally represented by formula (D): [ka] In the formula, R A1 and R A2 is as defined above for formula (A), and R D1 , R D2 , R D3 and R D4 is R B1 ~R B6 where e is an integer ranging from 1 to 8 (typically 2 to 4), f is approximately 1 or 2, T is lower alkylene or alkenylene (generally substituted or unsubstituted methyl or ethyl), CHR G1 , C(R G1 )2, O, S, NR G1 , PR G1 , O=PR G1 , Si(R G1 )2, BR G1 or As-R G1 (In the formula, R G1 is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, or alkoxy. D1 , R D2 , R D3 and R D4 If any of the parts are different from other R D1 , R D2, R D3 and R D4 The linkage may be attached to either moiety to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, and the linkage may contain a heteroatom or a functional group, for example, but not limited to, an ether, ester, thioether, amino, alkylamino, imino, or an anhydride moiety. The cyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono- or polyunsaturation, although monounsaturated cyclic groups are preferred. When substituted, the ring contains mono- or polysubstitution, where the substituents are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn (wherein n is 0 or 1, and Z * and Fn are as defined above, and are independently selected from the functional group (Fn) as described above.

[0123] The cyclic olefins included in formula (D) are from the norbornene family. As used herein, norbornene refers to any compound containing at least one norbornene or substituted norbornene moiety, such as, but not limited to, norbornene, substituted norbornene(s), norbornadiene, substituted norbornadiene(s), polycyclic norbornene, and substituted polycyclic norbornene(s). Norbornenes included in this group can generally be represented by formula (E): [ka] In the formula, R A1 and R A2 is as defined above for formula (A), T is as defined above for formula (D), and R E1 , R E2 , R E3 , R E4 , R E5 , R E6 , RE7 and R E8 is R B1 ~R B6 where "a" represents a single or double bond, f is approximately 1 or 2, and "g" is an integer from 0 to 5. When "a" is a double bond, R E5 , R E6 One of the two and R E7 , R E8 One of them does not exist.

[0124] Furthermore, R E5 , R E6 , R E7 and R E8 If any of the parts are different from other R E5 , R E6 , R E7 and R E8 The linkage may be attached to either moiety to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, and the linkage may contain a heteroatom or a functional group, for example, but not limited to, an ether, ester, thioether, amino, alkylamino, imino, or an anhydride moiety. The cyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono- or polyunsaturation, although monounsaturated cyclic groups are preferred. When substituted, the ring contains mono- or polysubstitution, where the substituents are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn (wherein n is 0 or 1, and Z * and Fn are as defined above, and are independently selected from the functional group (Fn) as described above.

[0125] More preferred cyclic olefins having at least one norbornene moiety have the formula (F): [ka] In the formula, RF1 , R F2 , R F3 and R F4 is R B1 ~R B6 wherein "a" represents a single bond or a double bond, "g" is an integer from 0 to 5, and when "a" is a double bond, R F1 , R F2 One of the two and R F3 , R F4 One of them does not exist.

[0126] Furthermore, R F1 , R F2 , R F3 and R F4 If any of the parts are different from other R F1 , R F2 , R F3 and R F4 The linkage may be attached to either moiety to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, and the linkage may contain a heteroatom or a functional group, for example, but not limited to, an ether, ester, thioether, amino, alkylamino, imino, or an anhydride moiety. The alicyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono- or polyunsaturation, although monounsaturated cyclic groups are preferred. The ring, when substituted, contains mono- or polysubstitution, where the substituents are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn (wherein n is 0 or 1, and Z * and Fn are as defined above, and are independently selected from the functional group (Fn) as described above.

[0127] One means for preparing hydrocarbyl- and functionally-substituted norbornenes is via a Diels-Alder cycloaddition reaction in which cyclopentadiene or a substituted cyclopentadiene is reacted with a suitable dienophile at elevated temperature to give a substituted norbornene adduct as generally shown in Reaction Scheme 4 below. [ka] In the formula, R F1 ~R F4 is as defined above for formula (F).

[0128] Other norbornene adducts can be prepared by pyrolysis of dicyclopentadiene in the presence of a suitable dienophile, where dicyclopentadiene is first pyrolyzed to cyclopentadiene, followed by Diels-Alder cycloaddition of cyclopentadiene with the dienophile to give the adduct shown in Scheme 5 below. [ka] In the formula, "g" is an integer from 0 to 5, and R F1 ~R F4 is as defined above for formula (F). Norbornadiene and its higher Diels-Alder adducts can also be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of acetylenic reactants, as shown in Scheme 6 below. [ka] In the formula, "g" is an integer from 0 to 5, and R F1 and R F4 is as defined above for formula (F).

[0129] Thus, examples of bicyclic and polycyclic olefins include, but are not limited to, dicyclopentadiene (DCPD); trimers and other higher oligomers of cyclopentadiene, such as, but not limited to, tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidene norbornene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene, and the like, and structural isomers, stereoisomers, and mixtures thereof. Further examples of bicyclic and polycyclic olefins include, but are not limited to, C2-C6 12Hydrocarbyl-substituted norbornenes include, for example, 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, and 5-butenyl-2-norbornene. Those skilled in the art will appreciate that the bicyclic and polycyclic olefins disclosed herein may consist of various structural isomers and / or stereoisomers, all of which are suitable for use in the present invention. Any reference herein to such bicyclic and polycyclic olefins includes any and all mixtures of such structural isomers and / or stereoisomers, unless specifically stated otherwise.

[0130] Preferred cyclic olefins include C5-C 24 Unsaturated hydrocarbons include C5-C containing one or more (typically 2-12) heteroatoms such as O, N, S, or P. 24 Cyclic hydrocarbons are also preferred. For example, crown ether cyclic olefins can contain multiple O heteroatoms throughout the ring, and these are within the scope of the present invention. Additionally, preferred cyclic olefins are C5-C containing one or more (typically two or three) olefins. 24 It is a hydrocarbon. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include, but are not limited to, cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

[0131] The cyclic olefin may also contain multiple (typically 2 or 3) rings. For example, the cyclic olefin may be monocyclic, bicyclic, or tricyclic. When the cyclic olefin contains two or more rings, the rings may be fused or unfused. Preferred examples of cyclic olefins containing multiple rings include norbornene, dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

[0132] Cyclic olefins may also be substituted, for example, C5-C6 olefins in which one or more (typically 2, 3, 4 or 5) of the hydrogens have been replaced with a non-hydrogen substituent. 24 The non-hydrogen substituents may be selected from those listed above. For example, functionalized cyclic olefins, i.e., C5-C olefins in which one or more (typically 2, 3, 4, or 5) of the hydrogen atoms have been replaced with a functional group, may be used. 24 Cyclic hydrocarbons are within the scope of the present invention. Suitable functional groups can be selected from those listed above. For example, cyclic olefins functionalized with alcohol groups can be used to prepare telechelic polymers with pendant alcohol groups. The functional groups on the cyclic olefins can be protected if they interfere with metathesis catalysis, and any of the protecting groups commonly used in the art can be used. Acceptable protecting groups can be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins include, but are not limited to, 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol, 5-n-hexyl-2-norbornene, and 5-n-butyl-2-norbornene.

[0133] Cyclic olefins incorporating any combination of the above features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the processes disclosed herein. Additionally, cyclic olefins incorporating any combination of the above features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the invention disclosed herein.

[0134] Cyclic olefins useful in the methods disclosed herein can be strained or unstrained. It will be understood that the amount of ring strain varies from cyclic olefin compound to cyclic olefin compound and depends on numerous factors, including ring size, the presence and nature of substituents, and the presence of multiple rings. Ring strain is one factor that determines the reactivity of a molecule toward ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring-opening reactions with olefin metathesis catalysts. Low-strain cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, generally have low reactivity. In some cases, ring-opening reactions of relatively unstrained (and therefore relatively unreactive) cyclic olefins may be possible when carried out in the presence of the olefin compounds disclosed herein. Furthermore, cyclic olefins useful in the invention disclosed herein can be strained or unstrained.

[0135] The resin composition of the present invention may contain multiple cyclic olefins. Multiple cyclic olefins can be used to prepare metathesis polymers from olefin compounds. For example, two cyclic olefins can be selected from the above-mentioned cyclic olefins to obtain a metathesis product incorporating two cyclic olefins. When two or more cyclic olefins are used, an example of the second cyclic olefin is a cyclic alkenol, i.e., a C5-C cyclic alkenol in which at least one of the hydrogen substituents is replaced with an alcohol or a protected alcohol moiety. 24 It is a cyclic hydrocarbon, which gives rise to a functionalized cyclic olefin.

[0136] The use of multiple cyclic olefins allows for further control over the location of functional groups within the product, particularly when at least one of the cyclic olefins is functionalized. For example, the density of crosslinking points can be controlled in the polymers and macromers prepared using the methods disclosed herein. Controlling the amount and density of substituents and functional groups also allows for control of the physical properties of the product (e.g., melting point, tensile strength, glass transition temperature, etc.). While control over these and other properties is possible in reactions using only a single cyclic olefin, it will be appreciated that the use of multiple cyclic olefins further expands the breadth of metathesis products and polymers that can be formed.

[0137] More preferred cyclic olefins are dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclohexenylnorbornene; endo,exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo,exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, etc.; and C2-C 12Hydrocarbyl-substituted norbornenes, such as 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, and 5-butenyl-2-norbornene. Even more preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher oligomers of cyclopentadiene, such as cyclopentadiene tetramer and cyclopentadiene pentamer, tetracyclododecene, norbornene, and C2-C6 olefins. 12 Included are hydrocarbyl-substituted norbornenes, such as 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, and 5-butenyl-2-norbornene.

[0138] While the present invention has been described in connection with specific embodiments thereof, it should be understood that the foregoing description and the following examples are illustrative of the scope of the invention and are not intended to limit it. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

[0139] Resin composition and article Commercially important ROMP resin formulations are generally based on readily available and inexpensive cyclic or polycyclic olefins, such as dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), and various other cycloalkenes. In one embodiment, the cyclic olefin composition used in preparing the resin and / or ROMP compositions of the present invention is dicyclopentadiene containing about 0%, or about 6%, or about 24%, or about 40%, or about 70% tricyclopentadiene.

[0140] Resin compositions according to the present invention generally include at least one cyclic olefin, which is combined with at least one metal carbene olefin metathesis catalyst to form a ROMP composition.

[0141] Resin compositions according to the present invention generally comprise at least one cyclic olefin, which is combined with at least one metal carbene olefin metathesis catalyst of the present invention to form a ROMP composition.

[0142] The ROMP compositions according to the present invention comprise at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin.

[0143] The ROMP compositions according to the present invention comprise at least one resin composition and at least one metal carbene olefin metathesis catalyst selected from the following: [ka]

[0144] The ROMP composition according to the present invention comprises at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and the at least one cyclic olefin is a norbornene derivative.

[0145] The ROMP composition according to the present invention comprises at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and the at least one cyclic olefin is dicyclopentadiene.

[0146] The ROMP composition according to the present invention comprises at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and the at least one cyclic olefin is tricyclopentadiene.

[0147] The ROMP composition according to the present invention comprises at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and the at least one cyclic olefin is tetracyclopentadiene.

[0148] The ROMP composition according to the present invention comprises at least one resin composition and at least one metal carbene olefin metathesis catalyst, wherein the resin composition comprises at least one cyclic olefin, and the at least one cyclic olefin is a norbornene derivative, such as 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, or 5-butenyl-2-norbornene.

[0149] In another embodiment, the resin composition of the present invention may additionally comprise at least one exogenous inhibitor. Exogenous inhibitors or "gel modification additives" used in the present invention are disclosed in U.S. Pat. No. 5,939,504, the contents of which are also incorporated herein by reference. Non-limiting examples of exogenous inhibitors or "gel modification additives" include water, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-Me-THF), diethyl ether ((C2H5)2O), methyl tert-butyl ether (CH3OC(CH3)3), dimethoxyethane (CHOCH2CHOCH3), diglyme (CH3OCHOCH2CHOCH3), trimethylphosphine (PMe3), triethylphosphine (PEt3), tributylphosphine ( PBu3), tri(orthotolyl)phosphine (Po-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), trioctylphosphine (POct3), triisobutylphosphine (Pi-Bu3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P Extrinsic inhibitors include triphenylphosphine (P(CF)), methyldiphenylphosphine (PMePh), dimethylphenylphosphine (PMePh), diethylphenylphosphine (PEtPh), trimethyl phosphite (P(OMe)), triethyl phosphite (P(OEt)), triisopropyl phosphite (P(Oi-Pr)), tributyl phosphite (P(OBu)), triphenyl phosphite (P(OPh)), and tribenzylphosphine (P(CHPh)), 2-cyclohexenone, and triphenylphosphine oxide. Preferred extrinsic inhibitors include triphenylphosphine, tricyclohexylphosphine, and tributylphosphine. The most preferred extrinsic inhibitor is triphenylphosphine. When formulated or mixed with the resin composition, the concentration of the extrinsic inhibitor typically ranges from 0.001 to 10 phr, specifically 0.01 to 5 phr, and more specifically 0.05 to 3 phr.The exogenous inhibitor can be added to the resin composition without a solvent or as an organic solution. One type of exogenous inhibitor can be used, or a combination of two or more different exogenous inhibitors can be used.

[0150] In another embodiment, the resin composition according to the present invention may additionally contain a hydroperoxide gel modifier. Hydroperoxide gel modifiers for use in the present invention are disclosed in International Application No. PCT / US2012 / 042850, the contents of which are also incorporated herein by reference. Non-limiting examples of hydroperoxide gel modifiers include tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, (2,5-dihydroperoxy)-2,5-dimethylhexane, cyclohexyl hydroperoxide, triphenylmethyl hydroperoxide, pinene hydroperoxide (e.g., Glidox® 500; LyondellBasell), and paramenthane hydroperoxide (e.g., Glidox® 300; LyondellBasell). More preferably, hydroperoxides suitable for use include tert-butyl hydroperoxide and cumene hydroperoxide. The hydroperoxide gel modification additive can be added to the reaction mixture without a solvent or as an organic or aqueous solution. A single hydroperoxide compound or a combination of two or more different hydroperoxide compounds can be used as the gel modification additive. Any concentration of hydroperoxide will delay the onset of the gel state in a particular metathesis polymerization. Advantageously, the use of a hydroperoxide gel modification additive has been found to substantially maintain the properties of the cured polymer, including the peak exotherm temperature and mechanical properties. While not necessarily limited, the hydroperoxide concentration is preferably 0.01 to 1000 equivalents relative to the catalyst. In other embodiments, the hydroperoxide concentration may be 0.1 to 20 equivalents relative to the catalyst. Generally, higher hydroperoxide concentrations result in longer pot life. In yet other embodiments, the hydroperoxide concentration may be 0.05 to 100 equivalents relative to the catalyst. In yet other embodiments, the hydroperoxide concentration may be 0.1 to 50 equivalents relative to the catalyst.

[0151] In another embodiment, the resin composition of the present invention may additionally contain at least one 5-alkenyl-2-norbornene as a pot life modifier. The 5-alkenyl-2-norbornene used in the present invention is disclosed in U.S. Pat. No. 5,204,427, and non-limiting examples thereof include 5-vinylbicyclo[2.2.1]hept-2-ene (5-vinyl-2-norbornene); 5-isopropenylbicyclo[2.2.1]hept-2-ene (5-isopropenyl-2-norbornene); 5-vinyl-4-vinylbicyclo[2.2.1]hept-2-ene (5-vinyl-4-vinyl-2-norbornene); 5-propenyl-bicyclo[2.2.1]hept-2-ene (5-vinyl-4-vinyl-2-norbornene); 5-Butenyl-bicyclo[2.2.1]hept-2-ene (5-butenyl-2-norbornene); 5-pentenyl-bicyclo[2.2.1]hept-2-ene (5-pentenyl-2-norbornene); and their monomethyl, monochloro, and dichloro substituted forms, including endo and exo isomers, and mixtures thereof. More preferred 5-alkenyl-2-norbornene(s) include the endo and exo isomers. Examples of suitable 5-alkenyl-2-norbornene pot life modifiers include 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, including their endo and exo isomers, and mixtures thereof. The most preferred 5-alkenyl-2-norbornene pot life modifier is 5-vinyl-2-norbornene (including its endo and exo isomers) and mixtures thereof. The 5-alkenyl-2-norbornene pot life modifier is typically present in the resin composition in an amount of about 0.01 phr to 1 phr. The 5-alkenyl-2-norbornene pot life modifier is preferably used at a concentration of about 0 phr, more preferably about 0.1 phr to 5 phr, and even more preferably about 0.1 phr to 3 phr. The 5-alkenyl-2-norbornene pot life modifier can be added to the resin composition without a solvent or as an organic solution. As the pot life modifier, one type of 5-alkenyl-2-norbornene pot life modifier may be used, or two or more different types of 5-alkenyl-2-norbornene pot life modifiers may be used in combination.

[0152] The resin composition of the present invention may optionally be formulated with additives. Suitable additives include, but are not limited to, gel modifiers, hardness modifiers, impact modifiers, elastomers, antioxidants, antiozonants, stabilizers, crosslinkers, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, plasticizers, pigments, flame retardants, dyes, fibers, and reinforcing materials (such as finishes, coatings, sized reinforcements and substrates treated with coupling agents, film formers, and / or lubricants). Furthermore, the amount of additive present in the resin composition may vary depending on the specific type of additive used. The concentration of the additive in the resin composition typically ranges, for example, from 0.001 to 85% by weight, specifically from 0.1 to 75% by weight, and even more specifically from 2 to 60% by weight.

[0153] The resin composition of the present invention may additionally comprise a crosslinking agent, such as a crosslinking agent selected from dialkyl peroxides, diacyl peroxides, and peroxyacids. Examples of such crosslinking agents are disclosed in U.S. Patent No. 5,728,785, the contents of which are incorporated herein by reference.

[0154] In another embodiment, the resin composition of the present invention may additionally comprise at least one cross-linking monomer, examples of which include the fused and linked polycyclic ring systems described in WO 0276613 A1 and U.S. Pat. No. 6,281,307 B1.

[0155] In another embodiment, the resin composition of the present invention may additionally contain at least one impact modifier. Suitable impact modifiers or elastomers include, but are not limited to, natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene-butadiene-styrene triblock rubber, random styrene-butadiene rubber, styrene-isoprene-styrene triblock rubber, styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate, and nitrile rubber.Preferred impact modifiers or elastomers are polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), styrene-ethylene / butylene-styrene copolymer Kraton G1651H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, ethylene-octene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon), hydrogenated styrene-ethylene / butylene-styrene copolymer Kraton Examples of impact modifiers according to the present invention include those manufactured by Addivant™ under the trade name Royaltuf® (e.g., Royaltuf® 498, Royaltuf® 485), the hydrogenated styrene-ethylene / butylene-styrene copolymer Kraton G1650M, and the styrene-butadiene block copolymer Kraton D1101; or those manufactured by Kraton Polymers under the trade name Kraton® (e.g., Kraton® G1650, Kraton® G1652, Kraton® FG1901, Kraton® FG1924). Such materials are typically used in resin compositions at concentrations of about 0.10 phr to 10 phr, more preferably about 0.1 phr to 5 phr. Various polar impact modifiers or elastomers can also be used.

[0156] In another embodiment, the resin composition of the present invention may additionally comprise at least one antioxidant. In another embodiment, the resin composition of the present invention may additionally comprise at least one antiozonant. Antioxidants and antiozonants include any antioxidant or antiozonant used in the rubber or plastics industries. "Index of Commercial Antioxidants and Antiozonants, Fourth Edition" is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company (Akron, Ohio 44316). Suitable stabilizers (i.e., antioxidants or antiozonants) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol (BHT); styrenated phenols such as Wingstay® S (Goodyear); 2- and 3-tert-butyl-4-methoxyphenol; alkylated hindered phenols such as Wingstay C (Goodyear); 4-hydroxymethyl-2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2,2′-methylenebis(4-methyl-6-tert-butylphenol); 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); 4,4′-methylenebis(2,6-di-tert-butylphenol); Cyanox® 53 (Cytec Industries Inc.) and Permanax Various bisphenols such as WSO; 2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4'-butylidenebis(6-tert-butyl-3-methylphenol); polybutylated bisphenol A; 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-methylenebis(2,6-dimethylphenol); 1,1'-thiobis(2-naphthol); methylene-bridged polyaklylphenols such as Ethyl Antioxidant 738; 2,2'-thiobis(4-methyl-6-tert-butylphenol);2,2'-Isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction products of p-cresol and dicyclopentadiene, such as Wingstay L; tetrakis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane, i.e., Irganox® 1010 (BASF); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, e.g., Ethanox® 330 (Albemarle Corporation); 4,4'-methylenebis(2,6-di-tert-butylphenol), e.g., Ethanox 4702 or Ethanox 4710; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, i.e., Good-rite® 3114 (Emerald Performance Materials), 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenyl phosphite), bis(2,4-di-tert-butyl)pentaerythritol) diphosphite, distearyl pentaerythritol diphosphite, phosphite-modified phenols and bisphenols such as Naugard® 492 (Chemtura Corporation), phosphite / phenol antioxidant blends such as Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate such as Irganox 1093;Examples of antioxidants and / or antiozonants include 1,6-hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate) such as Irganox 259, and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, i.e., Irganox 1076, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosphonite, diphenylamine, and 4,4'-diemthoxydiphenylamine. The antioxidants and / or antiozonants are typically used in a concentration of about 0.10 phr to 10 phr in the resin composition, and more preferably about 0.1 phr to 5 phr.

[0157] In another embodiment, the resin composition of the present invention may further comprise at least one filler. Suitable fillers include, for example, metal density modifiers, particulate density modifiers, organic fillers, inorganic fillers (e.g., microspheres), and macroparticle density modifiers (e.g., glass or ceramic beads). Metal density modifiers include, but are not limited to, powdered, sintered, exfoliated, flaked, ground, particulate, or granulated metals, metal oxides, metal nitrides, and / or metal carbides. Preferred metal density modifiers include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Particulate density modifiers include, but are not limited to, glass, metal, thermoplastic (either expandable or pre-expanded), or thermoset, and / or ceramic / silicate microspheres. Macroparticle density modifiers include, but are not limited to, glass, plastic, or ceramic beads; metal rods, chunks, pieces, or shot; hollow glass, ceramic, plastic, or metal spheres, balls, or tubes, etc. Organic fillers include, but are not limited to, polytetrafluoroethylene, polyethylene, ultra-high molecular weight polyethylene (PE-UHMWPE), polypropylene, polystyrene, acrylic, polyamide, aromatic polyamide, aramid fiber, carbon nanotubes, carbon fiber, graphite, carbon black, polysulfone, polyethersulfone, polyphenylsulfone, fluorinated ethylene propylene (FEP), polyether ethyl ketone (PEEK), polyvinylidene fluoride, polyamide imide, polyester, cellulose fiber, wood flour, wood fiber powder, particulates, flakes, fine powder, and shells. Inorganic fillers include, but are not limited to, powdered, particulates, flakes, fines, shells, and fibers of alumina trihydrate, barium sulfate, calcium sulfate, calcium carbonate, phosphate, talc, clay, mica, montmorillonite, molybdenum disulfide (MoS2), tungsten disulfide (WS2), boron nitrate, glass, silicates, aluminosilicates, magnesium oxide, zinc oxide, wollastonite, and barite.

[0158] In another embodiment, the resin composition of the present invention may further comprise at least one reinforcing material. Suitable reinforcing materials include those that, when incorporated into a polymer, increase the strength or stiffness of the polymer composite. The reinforcing material may be in the form of filaments, fibers, rovings, mats, woven fabrics, fabrics, knitted materials, textiles, cloth, or other known structures. Suitable reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers or fabrics (such as ultra-molecular weight polyethylene fabrics, including those manufactured by Honeywell under the trade name Spectra®), and polyoxazole fibers or fabrics (such as those manufactured by Toyobo Corporation under the trade name Zylon®). Reinforcing materials containing surface finishes, sizing, or coatings are particularly suitable for the described invention, including Ahlstrom glass roving (R338-2400), Johns Manville glass roving (StarROV®-086), Owens Corning roving (OCV366-AG-207, R25H-X14-2400, SE1200-207, SE1500-2400, SE2350-250), PPG glass roving (Hybon® 2002, Hybon® 2026), Toho Tenax® carbon fiber tow (HTR-40), and Zoltek carbon fiber tow (Panex® 35). Additionally, any woven fabric made using reinforcing materials containing surface finishes, sizing, or coatings is also suitable for the present invention. Advantageously, the present invention does not require costly processes to remove surface finishes, sizing, or coatings from the reinforcement material. Additionally, the glass fiber or woven glass may include, but is not limited to, A-glass, E-glass or S-glass, S-2 glass, C-glass, R-glass, ECR-glass, M-glass, D-glass, and quartz and silica / quartz. Preferred glass fiber reinforcements are those that include finishes formulated for use with epoxy resins, vinyl ester resins, and / or polyurethane resins.When formulated for use with a combination of these resin types, the reinforcement is sometimes described as "multi-compatible." During their manufacture, such reinforcements are generally treated with organosilane coupling agents containing vinyl, amino, glycidoxy, or methacryloxy functional groups (or various combinations thereof) and coated with a finish to protect the fiber surface and facilitate handling and processing (e.g., winding and weaving). The finish typically contains a mixture of chemical and polymeric compounds, such as film formers, surfactants, and lubricants. Particularly preferred glass reinforcements are those containing some amount of amino-functional silane coupling agents. Particularly preferred finishes are those containing epoxy and / or polyurethane film formers. Examples of preferred glass fiber reinforcements are Hybon® 2026, 2002, and 2001 (PPG) multi-compatible rovings; Ahlstrom R338 epoxy silane sized rovings; StarRov® 086 (Johns Manville) soft silane sized multi-compatible rovings; OCV™ 366, SE 1200, and R25H (Owens Corning) multi-compatible rovings; OCV™ SE 1500 and 2350 (Owens Corning) epoxy compatible rovings; and Jushi Group multi-compatible glass rovings (752 type, 396 type, 312 type, 386 type). Additional suitable polymer fibers and polymer fabrics may include, but are not limited to, one or more of polyester, polyamide (e.g., NYLON polyamide available from EI DuPont), aromatic polyamide (such as KEVLAR aromatic polyamide available from EI DuPont or P84 aromatic polyamide available from Lenzing Aktiengesellschaft), polyimide (e.g., KAPTON polyimide available from EI DuPont), polyethylene (e.g., DYNEEMA polyethylene available from Toyobo Co., Ltd.).Further suitable carbon fibers include, but are not limited to, AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42 / 850 from Hexcel Corporation; TORAYCA T300, T300J, T400H, T600S, T700S, T700G, T800H, T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J, M30S, M30G, and M40 from Toray Industries, Inc.; and HTS12K / 24K, G30-500 3k / 6K / 12K, G30-500 12K, G30-700 12K, G30-7000 24K F402, G40-800 from Toho Tenax Co., Ltd. 24K, STS 24K, HTR 40 F22 24K 1550tex; Grafil Inc.'s 34-700, 34-700WD, 34-600, 34-600WD and 34-600 size none; Cytec Industries' T-300, T-650 / 35, T-300C and T-650 / 35C. Additional suitable carbon fibers include, but are not limited to, AKSACA (A42 / D011), AKSACA (A42 / D012), Blue Star Starafil (10253512-90), Blue Star Starafil (10254061-130), SGL Carbon (C30 T050 1.80), SGL Carbon (C50 T024 1.82), Grafil (347R1200U), Grafil (THR 6014A), Grafil (THR 6014K), Hexcel Carbon (AS4C / EXP 12K), Mitsubishi (Pyrofil TR 50S 12L AF), Mitsubishi (Pyrofil TR 50S 12L AF), Toho Tenax (T700SC 12000-50C), Toray (T700SC 12000-90C), Zoltek (Panex 35 50K, sizing 11), Zoltek (Panex 35 50K, sizing 13). Further suitable carbon fabrics may include, but are not limited to, carbon fabrics by Vectorply (CL 1800) and Zoltek (Panex 35 UD Fabic-PX35UD0500-1220).Further suitable glass fibers may include, but are not limited to, Vectorply (E-LT 3500-10) based on PPG Hybon® 2026, Saertex (U14EU970-01190-T2525-125000) based on PPG Hybon® 2002, glass fabrics supplied by Chongqing Polycomp International Corp. (CPIC® fiberglass) (EKU 1150(0) / 50-600), and Owens Corning (L1020 / 07A06 Xweft 200tex).

[0159] The resin composition of the present invention may further comprise a sizing composition or may be used to improve adhesion to substrate materials sized with certain commercially available silanes commonly used in the industry. As known in the art, glass fibers are typically treated with a chemical solution (e.g., a sizing composition) immediately after their formation to reinforce the glass fibers and protect the mechanical integrity of the strands during processing and composite fabrication. Sizing treatments compatible with olefin metathesis catalysts and polydicyclopentadiene composites are described in U.S. Patent Nos. 6,890,650 and 6,436,476, the disclosures of which are incorporated herein by reference. However, these disclosures are based on the use of specialized silane treatments not commonly used in industrial glass manufacturing. In contrast, the present invention can improve the mechanical properties of polymer-glass composites sized with silanes commonly used in the industry.

[0160] Glass sizing formulations typically include at least one film-forming agent (typically a film-forming polymer), at least one silane, and at least one lubricant. A sizing formulation is considered compatible with the present invention and may generally be used herein if none of its components interferes with or substantially reduces the effectiveness of the metathesis catalyst or the olefin polymerization reaction.

[0161] Film formers compatible with ROMP catalysts include epoxies, polyesters, polyurethanes, polyolefins, and / or polyvinyl acetates. Other common film formers that do not adversely affect the performance of the olefin metathesis catalyst can be used. Film formers are typically used as nonionic aqueous emulsions. Two or more film formers may be used in a given sizing formulation to achieve the desired balance of glass processability and composite mechanical properties.

[0162] More specifically, the film former may include a low molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer having an average molecular weight (EEW) per epoxide group of less than 500, and / or a high molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer having an average molecular weight (EEW) per epoxide group of more than 500. Examples of suitable low molecular weight products include water-based epoxy emulsions manufactured by Franklin International, such as Franklin K8-0203 (EEW ​​190) and Franklin E-102 (EEW ​​225-275). Other examples of low molecular weight epoxy emulsions are available from Hexion, including EPI-REZ™ 3510-W-60 (EEW ​​185-215) and EPI-REZ™ 3515-W-60 (EEW ​​225-275). Further examples of low molecular weight epoxy emulsions are available from COIM and include Filco 309 (EEW ​​270) and Filco 306 (EEW ​​330). Further examples of low molecular weight epoxy emulsions are available from DSM and include Neoxil® 965 (EEW ​​220-280) and Neoxil® 4555 (EEW ​​220-260). Examples of suitable high molecular weight epoxy emulsion products include epoxy emulsions manufactured by Hexion, such as EPI-REZ™ 3522-W-60 (EEW ​​615-715).

[0163] Aqueous emulsions of modified epoxies, polyesters, and polyurethanes can also be used as film formers. Examples of suitable modified epoxy products include emulsions manufactured by DSM, such as Neoxil® 2626 (a plasticized epoxy with an EEW of 500-620), Neoxil® 962 / D (an epoxy ester with an EEW of 470-550), Neoxil® 3613 (an epoxy ester with an EEW of 500-800), Neoxil® 5716 (an epoxy novolac with an EEW of 210-290), Neoxil® 0035 (a plasticized epoxy ester with an EEW of 2500), and Neoxil® 729 (a lubricated epoxy with an EEW of 200-800). Further examples of modified epoxy emulsions are available from COIM and include Filco 339 (an unsaturated polyester epoxy with an EEW of 2000) and Filco 362 (an epoxy ester with an EEW of 530). Examples of suitable polyester products include emulsions manufactured by DSM, such as Neoxil® 954 / D, Neoxil® 2635, and Neoxil® 4759 (unsaturated bisphenol polyesters). Further suitable products from DSM include Neoxil® 9166 and Neoxil® 968 / 60 (adipate polyesters). Further examples of suitable products include emulsions manufactured by COIM, such as Filco 354 / N (unsaturated bisphenol polyesters), Filco 350 (unsaturated polyesters), and Filco 368 (saturated polyesters). Examples of suitable polyurethane products include emulsions manufactured by Bayer Material Science, such as Baybond® 330 and Baybond® 401.

[0164] Film-forming agents may also include polyolefins or polyolefin-acrylic copolymers, polyvinyl acetate, modified polyvinyl acetate, or polyolefin-acetic acid copolymers. Suitable polyolefins include, but are not limited to, polyethylene, polypropylene, polybutylene, and copolymers thereof, and polyolefins may be oxidized, maleated, or otherwise processed for effective film-forming. Examples of suitable products include emulsions manufactured by Michelman, such as Michem® Emulsion 91735, Michem® Emulsion 35160, Michem® Emulsion 42540, Michem® Emulsion 69230, Michem® Emulsion 34040M1, Michem® Prime 4983R, and Michem® Prime 4982SC. Examples of suitable products include emulsions manufactured by HB Fuller, such as PD 708H, PD 707, and PD 0166. Further suitable products include emulsions manufactured by Franklin International, such as Duracet® 637. Further suitable products include emulsions manufactured by Celanese, such as Vinamul® 8823 (plasticized polyvinyl acetate), Dur-O-Set® E-200 (ethylene-vinyl acetate copolymer), Dur-O-Set® TX840 (ethylene-vinyl acetate copolymer), and Resyn® 1971 (epoxy-modified polyvinyl acetate).

[0165] Preferred film formers include, but are not limited to, low and high molecular weight epoxies, saturated and unsaturated polyesters, and polyolefins such as Franklin K80-203, Franklin E-102, Hexion 3510-W-60, Hexion 3515-W-60, and Michelman 35160.

[0166] Nonionic lubricants may also be added to the sizing composition. Suitable nonionic lubricants compatible with ROMP compositions include esters of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide. If desired, more than one nonionic lubricant may be used in a given sizing formulation to achieve a desired balance of, for example, glass processability and composite mechanical properties.

[0167] Suitable lubricants may contain polyethylene glycol (PEG) units having an average molecular weight of 200 to 2000, preferably 200 to 600. These PEG units may be esterified with one or more fatty acids, including oleic acid, tall acid, lauric acid, stearic acid, etc. Particularly preferred lubricants include PEG 400 dilaurate, PEG 600 dilaurate, PEG 400 distearate, PEG 600 distearate, PEG 400 dioleate, and PEG 600 dioleate. Examples of suitable products include compounds manufactured by BASF, such as MAPEG® 400 DO, MAPEG® 400 DOT, MAPEG® 600 DO, MAPEG® 600 DOT, and MAPEG® 600 DS. Further suitable products include compounds manufactured by Zschimmer & Schwarz, such as Mulsifan 200 DO, Mulsifan 400 DO, Mulsifan 600 DO, Mulsifan 200 DL, Mulsifan 400 DL, Mulsifan 600 DL, Mulsifan 200 DS, Mulsifan 400 DS and Mulsifan 600 DS. Further suitable products include compounds manufactured by Cognis, such as Agnique® PEG 300 DO, Agnique® PEG 400 DO and Agnique® PEG 600 DO.

[0168] Suitable nonionic lubricants also include block copolymers of ethylene oxide and propylene oxide. Examples of suitable products include compounds manufactured by BASF, such as Pluronic® L62, Pluronic® L101, Pluronic® P103, and Pluronic® P105.

[0169] Cationic lubricants may also be added to the sizing composition. Cationic lubricants compatible with ROMP include modified polyethyleneimines, such as Emery 6760L manufactured by Pulcra Chemicals.

[0170] Silane coupling agents may optionally be added to the sizing composition, non-limiting examples of which include alkyl silanes, alkenyl silanes, and norbornenyl silanes, as well as methacrylate, acrylate, amino, or epoxy functionalized silanes.

[0171] Optionally, the sizing composition may include one or more additives to modify the pH of the sizing resin. One preferred pH adjuster is acetic acid.

[0172] The sizing agent composition may optionally contain other additives useful in glass sizing agent compositions. Such additives may include emulsifiers, antifoaming agents, cosolvents, biocides, antioxidants, and additives designed to improve the effectiveness of the sizing agent composition. The sizing agent composition may be prepared by any method and applied to a substrate material, such as glass fiber or glass fabric, used herein by any technique or method.

[0173] In another embodiment, the resin composition of the present invention may additionally contain at least one adhesion promoter. One type of adhesion promoter for use in the present invention is disclosed in International Application No. PCT / US2012 / 042850, the contents of which are also incorporated herein by reference. Non-limiting examples of adhesion promoters that can be used in the inventions disclosed herein are generally compounds containing at least two isocyanate groups (e.g., methylene diphenyl diisocyanate and hexamethylene diisocyanate). The adhesion promoter may be a diisocyanate, triisocyanate, or polyisocyanate (i.e., one containing four or more isocyanate groups). The adhesion promoter may be a mixture of at least one diisocyanate, triisocyanate, or polyisocyanate. In a more specific aspect of the present invention, the adhesion promoter includes or is limited to a diisocyanate compound or a mixture of diisocyanate compounds.

[0174] Generally, the adhesion promoter that can be used in the present invention can be any compound having at least two isocyanate groups.Suitable adhesion promoters include, but are not limited to, isocyanate compounds containing at least two isocyanate groups, and the compounds are selected from hydrocarbyl compounds, substituted hydrocarbyl compounds, heteroatom-containing hydrocarbyl compounds, substituted heteroatom-containing hydrocarbyl compounds, and functionalized hydrocarbyl compounds.As mentioned above, suitable hydrocarbyl adhesion promoter compounds generally include alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkaryl, and aralkyl compounds.Substituted heteroatom-containing and functionalized hydrocarbyl adhesion promoter compounds include the aforementioned hydrocarbyl compounds and variations thereof.

[0175] The adhesion promoter that can be used in the present invention can be an alkyl diisocyanate. Alkyl diisocyanates typically, but not necessarily, refer to linear, branched, or cyclic saturated or unsaturated hydrocarbon groups containing from 1 to about 24 carbon atoms, preferably diisocyanates containing from 2 to about 12 carbon atoms, and more preferably diisocyanates containing from 6 to 12 carbon atoms, such as hexamethylene diisocyanate (HDI), octamethylene diisocyanate, and decamethylene diisocyanate. Cycloalkyl diisocyanates typically contain cyclic alkyl groups having from 4 to 16 carbon atoms. Preferred cycloalkyl diisocyanates containing from 6 to about 12 carbon atoms include cyclohexyl, cyclooctyl, and cyclodecyl. The more preferred cycloalkyl diisocyanates are acetone, commonly known as 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, and isocyanato-[(isocyanatocyclohexyl)methyl]cyclohexane (H 12 It is formed as a condensation product with an isomer of MDI. 12 MDI is derived from the hydrogenated form of the aryl diisocyanate methylene diphenyl diisocyanate (MDI).

[0176] The adhesion promoter that can be used in the present invention can be an aryl diisocyanate. Aryl diisocyanate refers to an aromatic diisocyanate containing one aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (thus, different aromatic rings are bonded to a common group such as a methylene or ethylene moiety). Preferred aryl diisocyanates contain 5 to 24 carbon atoms, and particularly preferred aryl diisocyanates contain 5 to 14 carbon atoms. Exemplary aryl diisocyanates contain one aromatic ring or two fused or linked aromatic rings, such as phenyl, tolyl, xylyl, naphthyl, biphenyl, diphenyl ether, and benzophenone. Preferred aromatic diisocyanates include toluene diisocyanate, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI) (which may include any mixture of its three isomers, 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI).

[0177] The adhesion promoter that can be used in the present invention can be a polymer containing an isocyanate (e.g., a diisocyanate). An isocyanate-containing polymer refers to a polymer containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. Isocyanate-containing polymers generally require minimal solubility in the resin to provide improved mechanical properties. Preferred isocyanate-containing polymers include, but are not limited to, PM200 (poly-MDI), Lupranate® (BASF poly-MDI), Krasol® isocyanate-terminated polybutadiene prepolymers, such as Krasol® LBD2000 (TDI-based), Krasol® LBD3000 (TDI-based), Krasol® NN-22 (MDI-based), Krasol® NN-23 (MDI-based), and Krasol® NN-25 (MDI-based). Krasol® isocyanate-terminated polybutadiene prepolymer is available from Cray Valley.

[0178] The adhesion promoter that can be used in the present invention can be a trimer of alkyl diisocyanate and aryl diisocyanate. In the simplest form, any combination of polyisocyanate compounds can be trimerized to form an isocyanurate ring containing an isocyanate functional group. The trimer of alkyl diisocyanate and aryl diisocyanate can also be called an isocyanurate of alkyl diisocyanate or aryl diisocyanate. Preferred trimers of alkyl diisocyanate and aryl diisocyanate include, but are not limited to, hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl diisocyanate trimer, etc. More preferred adhesion promoters are toluene diisocyanate, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI) (including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI); liquid MDI; solid MDI; hexamethylene diisocyanate trimer (HDIt); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); liquid carbodiimide-modified 4,4'-MDI (Lupranate® MM103); liquid MDI (Lupranate® MI); liquid MDI (Mondur® ML); and liquid MDI (Mondur® MLQ).An even more preferred adhesion promoter is methylene diphenyl diisocyanate (MDI), such as any mixture of its three isomers 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI; liquid MDI; solid MDI; hexamethylene diisocyanate trimer (HDIt); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4'-methylenebis(cyclohexylisocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); liquid carbodiimide-modified 4,4'-MDI (Lupranate® MM103); liquid MDI (Lupranate® MI); liquid MDI (Mondur® ML); liquid MDI (Mondur® MLQ).

[0179] Any concentration of adhesion promoter that improves the mechanical properties of the olefin composite (e.g., ROMP polymer composite) is satisfactory for the present invention. Generally, suitable amounts of adhesion promoter range from 0.001 to 50 phr, specifically 0.05 to 10 phr, more specifically 0.1 to 10 phr, and even more specifically 0.5 to 4.0 phr. One or more adhesion promoters can be used in the present invention.

[0180] Further adhesion promoters suitable for use in the present invention have the formula Fn-(A) n -Si(Y * ) 3 functional silanes (wherein Y *is selected from a halide (preferably chloride) or OR; Fn is a functional group selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene; A is a divalent linking group selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; n is 0 or 1; and R is a hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, preferably selected from lower alkyl, more preferably methyl, ethyl, or isopropyl, and a peroxide selected from dialkyl peroxide and diaryl peroxide.

[0181] Additional adhesion promoters and methods of use that may be used in the present invention include those disclosed in International Application No. PCT / US00 / 03002, the contents of which are incorporated herein by reference.

[0182] Articles include, but are not limited to, those formed by standard manufacturing techniques, including casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), pouring, vacuum impregnation, surface coating, filament winding, and other known methods useful for producing polymeric and / or polymeric composite articles. Furthermore, the compositions and articles of manufacture of the present invention are not limited to single polymer surface interfaces, but also include multilayers and laminates containing multiple polymer surface interfaces. The present invention is also suitable for producing articles by infusing resin into porous materials. Such porous materials include, but are not limited to, wood, cement, concrete, open-cell reticulated foams and sponges, paper, cardboard, felt, ropes or braids of natural or synthetic fibers, and various sintered materials. In addition, other manufacturing techniques include, but are not limited to, cell casting, dip casting, continuous casting, embedding, potting, encapsulation molding, film or solvent casting, gate casting, mold casting, slush casting, extrusion, mechanical foaming, chemical foaming, physical foaming, compression or matched die molding, spraying, spray-up, vacuum-assisted resin transfer molding (VAR™), Seeman composite resin injection molding process (SCRIMP), blow molding, in-mold coating, in-mold painting or injection, vacuum forming, reinforced reaction injection molding (RRIM), structural reaction injection molding (SRIM), thermal expansion transfer molding (TERM), resin injection recirculation molding (RICM), controlled atmospheric pressure resin infusion (CAPRI), and hand-build molding. For manufacturing techniques requiring the use of RIM or impingement-type mixheads, including, but not limited to, RIM, SRIM, and RRIM, the article can be molded using a single mixhead or multiple mixheads and multiple material injection streams (e.g., two resin streams and one catalyst stream). Because the present invention allows for faster cycle times and higher molding temperatures (e.g., molding temperatures above 90°C) using any of the aforementioned manufacturing techniques, it may be necessary to mold the ROMP compositions of the present invention under high pressure or vacuum to prevent defects caused by mixing problems and / or trapped gases.

[0183] Furthermore, the present invention also allows for the creation of articles of manufacture of any configuration, weight, size, thickness, or geometry. Examples of articles of manufacture include, but are not limited to, any molded or shaped article used as an aerospace part, a marine part, an automotive part, a sporting goods part, an electrical and industrial part, a medical part, a dental part, or a military part. In one embodiment, the article may be a turbine part used in aircraft or general power generation. In one embodiment, the turbine part may include, but is not limited to, one or more of an inlet, a pylon, a pylon fairing, an acoustic panel, a thrust reverser panel, a fan blade, a fan housing, a bypass duct, an aerodynamic cowl, or an airfoil part. In one embodiment, the article may be a turbine blade part or a turbine blade. In one embodiment, the article may be a wind rotor blade, a tower, a spar cap, or a nacelle of a wind turbine. In one embodiment, the article may be an airframe part. Examples of aerospace parts may include, but are not limited to, one or more of a fuselage surface, a wing, a fairing, a door, an inspection panel, an aerodynamic control surface, or a stiffener. In one embodiment, the article may be an automotive part. Examples of automotive parts may include, but are not limited to, one or more of a body panel, a fender, a spoiler, a truck bed, a protection plate, a hood, a longitudinal rail, a pillar, or a door. Examples of industrial parts may include, but are not limited to, one or more of an oil and gas riser platform, a crash protection structure; a bridge, a pipe, a pressure vessel, a utility pole, a coil, a container, a tank, a liner, a containment vessel, an article applied in a corrosive environment (e.g., chlorine-alkaline, caustic, acid, saltwater, etc.), a centralizer (e.g., an oil field centralizer), an electrolytic cell cover, a reinforced structure for concrete buildings and roads, or a radiator. Examples of electrical parts may include, but are not limited to, one or more of a wound article such as a coil or an electric motor, or an insulating device. In one embodiment, the article may be an eddy current shielding component or any electromagnetic radiation shielding component of a magnetic resonance imaging system.In one embodiment, the article can be a military component, including, but not limited to, ballistic armor for crew or vehicles or ballistic structures for protecting personnel or equipment. In one embodiment, the article can be a sporting goods component, including, but not limited to, an arrow shaft, a tennis racket frame, a hockey stick, a compound bow limb, or a golf club shaft. In one embodiment, the article can be an object used in offshore applications, which is at least partially coated with the ROMP composition of the present invention. The object can include, but is not limited to, pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, vessels, drums, manifolds, risers, field fittings, Christmas tree structures (oil field Christmas trees, subsea Christmas trees), jumpers, spool pieces, pipeline terminations (PLETs), pipeline end manifolds (PLEMs), robotic components, devices, and vehicles used in subsea applications, subsea doghouses, and other subsea structures and equipment. Other non-limiting examples of offshore applications include insulating materials (eg, thermal insulation) and field joint coating materials.

[0184] In a preferred embodiment, the metathesis reactions disclosed herein are carried out under a dry, inert atmosphere. Such an atmosphere can be created using any inert gas, including gases such as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalytic activity, and reactions carried out under an inert atmosphere are typically carried out at relatively low catalyst loadings. The reactions disclosed herein can also be carried out under oxygen-containing and / or water-containing atmospheres; in one embodiment, the reactions are carried out under ambient conditions. However, the presence of oxygen or water in the reaction may necessitate the use of higher catalyst loadings compared to reactions carried out under an inert atmosphere. The reactions disclosed herein can also be carried out under reduced pressure if the vapor pressures of the reactants permit.

[0185] The reactions disclosed herein can be carried out in a solvent, and any solvent inert to cross-metathesis can be used. Generally, solvents that can be used in metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Examples of solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. In a preferred embodiment, the reactions disclosed herein are carried out neat, i.e., without the use of a solvent.

[0186] It will be appreciated that the temperature at which the metathesis reaction according to the methods disclosed herein is carried out can be adjusted as needed over a wide temperature range. With highly active metathesis catalysts, olefin metathesis can occur at temperatures as low as -78°C. With more latent catalysts, olefin metathesis may not be observed until temperatures of -40°C, -10°C, 0°C, 10°C, 20°C, 25°C, 35°C, 50°C, 70°C, 100°C, or 150°C. In one embodiment, the reaction is carried out at a temperature of at least about 35°C, and in another embodiment, the reaction is carried out at a temperature of at least about 50°C. In certain embodiments, the polymerization can be completed more quickly by filling the mold or preform with the resin and catalyst at a temperature close to room temperature (e.g., about 10-45°C, preferably 15-40°C, more preferably 20-35°C) and then heating to a higher temperature (e.g., about 50-200°C, preferably 70-150°C, more preferably 90-120°C) over a period of time. In certain embodiments, the cycle time can be faster if the mold or preform is preheated to a temperature significantly higher than room temperature (e.g., about 50-250°C, or about 50-200°C, or about 50-150°C, or about 40-80°C, or about 40-60°C, or about 60-80°C, or about 50-100°C, or about 100-150°C, or about 150-200°C) and then quickly filling with the resin and catalyst.

[0187] experiment Overview - Materials and Methods In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperatures, etc.), but some experimental error and deviation should be accounted for. The examples should not be construed as limiting the invention described herein.

[0188] All reactions involving metal complexes were carried out 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).

[0189] Catalyst starting material C627 (RuCl2(sIMes)(CHC6H4OPr i)) [CAS301224-40-8], trans-748 (trans-RuCl2(sIMes)(phenylindenylidene)(pyridine)) [CAS103126-76-6], trans-C848 (trans-RuCl2(sIMes)(CHPh)(PPh3)) [CAS246047-72-3], trans-727 (trans-RuCl2(sIMes)(CHPh)(pyridine)2) [CAS357186-58-4], trans-C719v (trans-RuCl2(sIMes)(t-butylvinylidene)(pyridine)2) [CAS496869-36-4], tra ns-C771 (trans-RuCl(sIMes)(CHPh)(P(n-Bu)) [CAS 388095-35-0], trans-C835 (trans-RuCl(sIMes)(phenylindenylidene)(PPh(Et)) [CAS 1403376-05-5], trans-C827 (RuCl(sIMes)(3-methyl-2-butenylidene)(PCy)) [CAS 253688-91-4], and trans-C705 (RuCl(sIMes)(3-methyl-2-butenylidene)(pyridine)) [CAS 507274-22-8] were prepared using known methods.

[0190] Ultrene® 99 dicyclopentadiene (DCPD) was obtained from Cymetech Corporation. Modified DCPD-based resins containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologues) (DCPD-HT) were prepared by heat treating Ultrene® 99 DCPD generally as described in U.S. Pat. No. 4,899,005.

[0191] 1 H and 13 C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are reported in ppm downfield from Me4Si using the residual solvent peaks (CDCl3- (δ 7.24 ppm; CD2Cl2- (δ 5.32 ppm)) as internal standards. 31P NMR was performed in a coaxial NMR tube using triphenylphosphine in C6D6 as the standard (δ -6.0 ppm). Spectra were analyzed and processed using Vnmr J 4.0 software.

[0192] In the examples, the following abbreviations are used: [Table 1-1] [Table 1-2] [Table 1-3] [Example]

[0193] Example 1 [ka]

[0194] trans-RuCl2(sIMes)(CHC6H4Oi-Pr)(Ph2P(OMe)), trans-C843: In a one-neck round-bottom flask equipped with a magnetic stir bar, C627 (1.0 g, 1.59 mmol) was dissolved in degassed DCM (25 mL) under nitrogen, and methyl diphenylphosphinite (0.379 g, 1.75 mmol) was added. The flask was stoppered with a gas adapter. The mixture was degassed three times with N2 / vacuum cycles. After stirring at room temperature for 1 h, the solvent was removed under high vacuum. To the residue was added degassed methanol (75 mL). A purple solid was collected by vacuum filtration through a fritted funnel. The solid was further dried under high vacuum for 16 h. Yield: 0.7 g (69%). 1H NMR(400MHz,CDCl3,ppm):δ19.60(s,Ru=CH,1H),7.95(dd,J=8Hz,J=2Hz,1H),7.22-6.80( b,13H),6.66(b,1H),6.44(d,J=8Hz,1H),6.25(t,J=8Hz,1H),6.02(b,1H),4.42(septet,J =6Hz,OCHMe2,1H),4.13-3.78(b,NCH2CH2N,4H),3.11(d,J=7Hz,OCH3,3H),2.72(b,3H),2 .58(b,3H),2.52(b,3H),2.30(s,3H),2.03(b,3H),1.85(s,3H),1.49(b,3H),1.29(b,3H). 31 P NMR (162MHz, CDCl3): δ135.7(s).

[0195] Example 2 [ka]

[0196] cis-RuCl(sIMes)(CHCHOi-Pr)(PhP(OMe)), cis-C843: In a single-neck round-bottom flask, C627 (35.0 g, 56 mmol) was dissolved in degassed CHCl (200 mL) under nitrogen, and methyl diphenylphosphinite (50 g, 231 mmol) was syringe-injected. The flask was connected to a Friedrich condenser, which was then fitted with a vacuum / nitrogen line. The mixture was degassed three times with vacuum / nitrogen. The flask was heated using an oil bath. The oil bath temperature was maintained at 50 °C for 40 h and then cooled to room temperature. The solvent was removed under high vacuum. The residue was dissolved in a minimal amount of CHCl and loaded onto the top of a SiO gel column (D × H: 4 × 3 inches) and eluted with CHCl. ​​The red band on the column was rinsed with methanol. The solvent was removed on a rotary evaporator to give a green solid, which was further purified by recrystallization from CH2Cl2 / hexane. Yield: 15 g (32%). 11H NMR (400 MHz, C6D6, ppm): δ 16.45 (d, J = 24 Hz, Ru=CH, 1H), 10.11 (dd, J = 8 Hz, J = 2 Hz, 1H), 7.55 (t, J = 9 Hz, 2H), 7.20 (ddd, J = 9 Hz, J = 7 Hz, J = 2 Hz, 1H), 7.00 (m, 3H), 6.87 (dt, J = 2 Hz, J = 8 Hz, 2H), 6.79 (t, J = 8 Hz, 1H), 6.75 - 6.65 (m, 3H), 6.61 (d, J = 10 Hz), 6.20 (m, 2H), 4.11 (septet, J = 6 Hz, -OCHMe2, 1H), 3.50 - 3.06 (m, 4H), 3.38 (d, J = 10 Hz, -OCH3, 3H), 2.92 (s, 3H), 2.51 (s, 3H), 2.45 (s, 3H), 2.33 (s, 3H), 1.95 (s, 3H), 1.91 (s, 3H), 1.25 (d, J = 6 Hz, 3H, OCH(CH3)(CH3), 3H), 0.97 (d, J = 6 Hz, 3H, OCH(CH3)(CH3), 3H). 31 31P NMR (162 MHz, C6D6, ppm): δ 140.9 (b).

[0197] Example 3 [Chemical formula]

[0198] cis-RuCl(sIMes)(CHCHOi-Pr)(PhP(OMe)), cis-C797: A round-bottom flask under nitrogen was charged with C627 (15.0 g), degassed CHCl (100 mL), and a magnetic stir bar, followed by the addition of the phosphonite PhP(OMe) (4.1 g). The solution was stirred for 3.7 h, and a second portion of the phosphonite PhP(OMe) (2.05 g) was added. The solution was stirred for an additional 2 h and then concentrated on a rotary evaporator. A silica gel plug column (D × H: 4 × 2.5 inches) was prewetted with CHCl. ​​A light vacuum was used to aid in elution. The crude product was loaded onto the top of the column. The initial eluent was CHCl, and the green fraction was collected. This was confirmed by NMR to be C627. The yellow fraction following the green fraction appeared to be the oxidized derivative of the phosphonite. The eluent was then changed to a gradient mixture of CHCl / EtOAc. The brown band containing the product was collected. The solvent was removed by rotary evaporation, and the residue was recrystallized from CHCl / heptane. A black crystalline solid was obtained (3.1 g). 1 H NMR(400MHz,CD2Cl2,ppm):δ15.83(d,J=24Hz,1H,Ru=CH),9.16(dd,J=8Hz,J=2Hz,1H),7.51(m,1H),7.25(m,1H),7.15(m,2H) ,7.02-6.88(m,5H),6.66(s,1H),6.61(d,J=8Hz,1H),6.14(s,1H),4.49(septet,J=6Hz,1H,CHMe2),4.02-3.62(m,4H,CH2CH2 ), 3.33 (d, J = 11 Hz, 3H, OCH3), 3.05 (d, J = 12 Hz, OCH3), 2.67 (s, 3H, mesitylmethyl), 2.62 (s, 3H, mesitylmethyl), 2.46 (s, 3H, mesitylmethyl), 2.33 (s, 3H, mesitylmethyl), 2.22 (s, 3H, mesitylmethyl), 1.95 (s, 3H, mesitylmethyl), 1.46 (d, J = 6 Hz, 3H, CH(CH3)2), 1.19 (d, J = 6 Hz, 3H, CH(CH3)2). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ163.84(b).

[0199] Example 4 [ka]

[0200] trans-RuCl2(sIMes)(CHPh)(Ph2P(OMe)), trans-C785: In a round-bottom flask, trans-C727 (4.35 g, 6.0 mmol) was dissolved in degassed CHCl2 (50 mL) under nitrogen with a magnetic stir bar. The flask was stoppered with a gas adapter. Methyl diphenylphosphinite (2.6 g, 12 mmol) was syringed into the flask under a stream of nitrogen. The green solution immediately turned brown. Stirring was continued at room temperature for 1 h. The liquid was removed under high vacuum to give a mixture of a black oil and a brown crystalline material. The flask was cooled with liquid nitrogen, and the resulting solid was crushed with a spatula. Hexane (50 mL) was added, and the solvent was reduced on a rotary evaporator. The light pink solid was collected on a fritted funnel by vacuum filtration and washed twice with hexane (2 × 25 mL). The solid was dried under high vacuum for 16 hours. Yield: 2.91 g (62%). 1 H NMR(400MHz,C6D6,ppm):δ19.33(s,1H,Ru=CH),7.86(d,J=8Hz,2H),7.33(m,4H),7.13(t,J=8Hz,1H),7.10-6.88(m,6H),6.83(s,2H),6. 80(m,2H),6.32(s,2H),3.46-3.38(m,2H),3.34-3.25(m,2H),3.29(d,J=12Hz,3H),2.79(s,6H),2.39(s,6H),2.17(s,3H),1.90(s,3H). 31 P NMR (162MHz, C6D6, ppm): δ132.5(s).

[0201] Example 5 [ka]

[0202] cis-RuCl2(sIMes)(CHPh)(Ph2P(OMe)), cis-C78 5: In a single-neck round-bottom flask under nitrogen, trans-C848 (10.0 g, 11.8 mmol) was dissolved in 1,2-dichloroethane (50 mL) with a magnetic stirrer. Methyl diphenylphosphinite (5.1 g, 23.6 mmol) was added via syringe. The flask was connected to a gas adapter and then degassed three times with N2 / vacuum cycles. The flask was connected to a nitrogen line and heated to 70 °C in an oil bath. Heating was continued for 16 h. The oil bath was removed, and the flask was allowed to cool to room temperature. The solvent was removed by rotary evaporation. CHCl2 and hexane (100 mL each) were added to the residue. The solvent was reduced by half on a rotary evaporator, revealing a solid. The solid was collected by vacuum filtration into a fritted funnel. The solid was recrystallized from CH2Cl2 / methanol and dried under high vacuum for 16 hours to give a bluish-gray solid (7.0 g). 1 H NMR(400MHz,CD2Cl2,ppm):δ15.41(d,J=25Hz,1H,Ru=CH),7.45-6.95(m,17H),6.65(s,1H),6.10(s,1H),4.04-3.90(m,3H),3.74-3.66(m,1H),3.59 (d,J=10Hz,3H,P(OCH3)),2.77(s,3H,ArCH3),2.69(s,3H,ArCH3),2.39(s,3H,ArCH3),2.37(s,3H,ArCH3),2.11(s,3H,ArCH3),1.95(s,3H,ArCH3). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ132.32,132.30.

[0203] Example 6 [ka]

[0204] trans-RuCl(sIMes)(benzylidene) (PhP(OMe)), trans-C139: To a round-bottom flask containing a magnetic stir bar under N2, trans-C727 (14.54 g, 20 mmol) was added degassed CHCl (100 mL). The phosphonite PhP(OMe)2 (3.74 g, 22 mmol) was added. The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 15 min. The solvent was removed under high vacuum to give a crude solid. This crude solid was dissolved in CHCl2 and passed through a silica gel plug (D x H: 4" x 3"). The first fraction was eluted with CHCl2, and the second fraction was eluted with EtOAc. The first fraction was concentrated on a rotary evaporator to a slurry, which was filtered and washed with heptane to give a yellowish-brown solid (4.9 g). 1 H NMR (400MHz, CDCl3, ppm): δ18.81(s,1H),765-7.63(m,2H),7.37-7.41(m,1H),7.21-7.17(m,1H),7.01-6.96(m,6H),6.85(s,2H),6. 35(s,2H),4.07-4.05(m,2H),3.94-3.92(m,2H),3.13(d,J=12Hz,6H,P(OCH3)2),2.59(s,6H),2.25(s,3H),2.18(s,6H),1.99(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ157.04(s).

[0205] Example 7 [ka]

[0206] cis-RuCl(sIMes)(benzylidene)(PhP(OMe)), cis-C739: (See trans-RuCl(sIMes)(benzylidene)(PhP(OMe)), trans-C739 above.) The second fraction was concentrated by rotary evaporation to a slurry, which was filtered and washed with heptane to give a blue-purple solid (2.2 g). This crude solid was dissolved in degassed CHCl (10 mL) and subsequently precipitated with degassed heptane (100 mL). A blue-purple crystalline material formed, which was filtered, washed with heptane, and dried under high vacuum. Yield: 1.9 g. 1 H NMR (400MHz, CDCl3, ppm): δ15.24(d,J=22.7Hz,1H),7.81-7.79(m,2H),7.48-7.44(m,1H),7.22-7 .18(m,2H),7.17-7.13(m,1H),7.05-7.01(m,2H),6.98-6.96(m,2H),6.94-6.89(m,2H),6.86(s,1 H),6.12(s,1H),4.00-3.94(m,1H),3.92-3.85(m,2H),3.73-3.69(m,1H),3.33(d,J=11Hz,3H),3. 08(d,J=11Hz,3H),2.68(s,3H),2.62(s,3H),2.55(s,3H),2.31(s,3H),2.10(s,3H),2.05(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ158.40(s).

[0207] Example 8 [ka]

[0208] trans-RuCl(sIMes)(benzylidene) (PhP(OPh)), trans-C847: To a round-bottom flask containing a magnetic stir bar under nitrogen was added trans-C727 (7.27 g, 10 mmol) and degassed CHCl (50 mL). Phosphite PhP(OPh) (3.06 g, 11 mmol) was added via syringe. The reaction vessel was evacuated and backfilled with N (3x). The reaction was stirred under N at ambient temperature (20-25 °C) for 15 min. The solvent was removed under high vacuum. Degassed toluene (50 mL) was added and the reaction vessel was evacuated and backfilled with N (3x). The solvent was removed under high vacuum. The crude material was dissolved in CHCl and passed through a silica gel plug (D x H: 3" x 1"). The silica gel plug was washed with CH2Cl2, the organic material was concentrated, and heptane (50 mL) was added to give a black oil and a supernatant. Upon settling, a solid appeared. This solid was filtered and washed with heptane to give a brown solid (0.7 g). 1 H NMR(400MHz,CD2Cl2,ppm):δ18.80(s,1H),7.71(m,2H),7.44(m,1H),7.27(m,2H),7.13-7.02(m,10H),6.92(s,2H),6.85(m,2H), 6.78(m,1H),6.44(m,2H),6.38(s,2H),4.10-4.03(m,2H),3.96-3.90(m,2H),2.58(s,6H),2.37(s,3H),2.22(s,6H),2.00(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ134.58(s).

[0209] Example 9 [ka]

[0210] trans-RuCl(sIMes)(phenylindenylidene) (PhP(OMe)), trans-C: A round-bottom flask containing a magnetic stir bar was charged with trans-C 2Py (9.06 g, 10 mmol) under nitrogen and heptane (150 mL) was added. Phosphinit PhP(OMe) was added via syringe. After stirring for 1 h, the suspension gradually turned red. The purple solid was collected by vacuum filtration using a fritted funnel. The solid was then dried under high vacuum for 2 h. Yield: 8.6 g. 1 H NMR(400MHz,CD2Cl2,ppm):δ8.09(d,J=7Hz,1H),7.60(m,2H),7.54(m,1H),7.41(m,2H),7.32-6.98(m,14H),6.61(s,1H),6.44 (b,1H),6.08(b,1H),4.16-3.80(m,4H),3.23(d,J=12Hz,3H),2.72(s,6H),2.43(s,3H),2.20(s,3H),2.05(s,3H),1.83(s,3H). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ122.1(s).

[0211] Example 10 [ka] cis-RuCl(sIMes)(phenylindenylidene) (PhP(OMe)), cis-C885: Under nitrogen, a round-bottom flask containing a magnetic stir bar was charged with trans-C748·2Py (27.18 g, 30 mmol) and degassed heptane (500 mL). Phosphite PhP(OMe) (6.8 g, 31.5 mmol) was added via syringe. The reaction vessel was evacuated and backfilled with N2 (3x). The mixture was stirred under N2 at ambient temperature (20-25 °C) for 1 h. Some undissolved starting material remained, so degassed CHCl2 (250 mL) was added to dissolve all solids. The solution was passed through a silica plug (D x H: 2.5" x 1.5") and eluted with CHCl2, removing the first red band of material, which was trans-C885. The second band was then removed using EtOAc as the eluent, which was concentrated and filtered to give brown crystals of cis-C885 (8.49 g). 1 H NMR(400MHz,CD2Cl2,ppm):δ8.78(dd,J=8Hz,J=1Hz,1H),7.52-7.24(m,8H),7.13-6.89(m,9H),6.75(m,2H),6.43(s,1H),6.40(s,1H),6.24 (s,1H),6.11(s,1H),3.98-3.63(m,4H),3.66(d,J=10Hz,3H),2.79(s, 3H),2.56(s,3H),2.54(s,3H),2.21(s,3H),1.95(s,3H),1.66(s,3H). 31 P NMR(161.8MHz,CD2Cl2,ppm):δ133.3(s)

[0212] Example 11 Isomerization of cis-C885 to trans-C885 [ka]

[0213] Cis-C885 (50 mg) was dissolved in 0.5 mL of CD2Cl2 in an NMR tube. Isomerization was monitored by NMR (Figure 1, where C885B is cis-C885 and C885A is trans-C885).

[0214] Example 12 [ka]

[0215] trans-RuCl2(sIMes)(phenylindenylidene) (Ph2P(OPh)), trans-C947: Under nitrogen, a round-bottom flask containing a magnetic stir bar was charged with trans-C748·2Py (90.6 g, 100 mmol) and degassed toluene (1 L). Phosphite Ph2P(OPh) (30.58 g, 110 mmol) was added via syringe. The reaction vessel was evacuated and refilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 1 h. The solvent was removed under high vacuum. Degassed CHCl2 (1 L) was added, and the reaction vessel was evacuated and refilled with N2 (3x). The solvent was removed under high vacuum, and the solid was allowed to stand in the flask for 2 days. Degassed methanol was added, and the precipitate was filtered and washed with methanol. The crude solid was dried under high vacuum. The crude solid was dissolved in CHCl and filtered through a silica plug (D×H: 3″×1″). The plug was washed with CHCl (500 mL). The combined organic eluents were concentrated to half the volume, and degassed heptane (500 mL) was added. The solution was then further reduced under high vacuum to give a slurry, which was filtered and washed with heptane. The solid was dried under high vacuum to give trans-C947 (67 g). 1H NMR(400MHz, CDCl3, ppm): δ8.18(d,J=7.4Hz,1H),7.58-7.56(m,2H),7.51-7.47(m,1H),7 .37-7.33(m,2H),7.24-7.15(m,7H),7.03-6.94(m,8H),6.78-6.74(m,2H),6.71(s,1H),6 .66-6.62(m,1H),6.55-6.53(m,2H),6.43(s,1H),6.07(s,1H),4.07-4.13(m,2H),3.82-3 .95(m,2H),2.70(s,3H),2.66(s,3H),2.40(s,3H),2.25(s,3H),2.01(s,3H)1.80(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ126.58(s).

[0216] Example 13 [ka]

[0217] cis-RuCl(sIMes)(phenylindenylidene)(PhP(OPh)), cis-C947: (See trans-RuCl(sIMes)(phenylindenylidene)(PhP(OPh)), trans-C947 above). The silica gel plug from the trans-C947 synthesis was then washed with ethyl acetate to remove the second band, which was the cis product. The eluate was concentrated under high vacuum to give brown crystals. The slurry was filtered, and the filtrate was concentrated to give the cis product as brown crystals. The crystals were washed with EtOAc and kept under high vacuum for 16 hours. Yield: 15.0 g. 1H NMR (400MHz, CDCl3, ppm): δ9.11(d,J=0.8Hz,1H),7.59-7.55(m,2H),7.49-7.45(m,1H),7.36-7.2 7(m,5H),7.22-7.18(m,2H),7.12-7.04(m,3H),7.03-6.99(m,3H),6.88-6.86(m,1H),6.82(s,1H) ,6.67-6.64(m,4H),6.37-6.35(m,2H),6.26(m,2H),6.23(s,1H),6.07(s,1H),3.96-3.93(m,1H), 3.74-3.64(m,3H),2.77(s,3H),2.66(s,3H),2.29(s,3H),2.12(s,3H),2.00(s,3H),1.58(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ137.68(s).

[0218] Cis-trans isomerization of C947 in solution [ka]

[0219] Solution preparation. An appropriate amount of anthracene (approximately 5 mg) was dissolved in either 1 mL of CD2Cl2 or 1 mL of C6D6. Once the anthracene was completely dissolved, the solution was transferred to a vial containing the appropriate amount of catalyst (approximately 20 mg). Catalyst solubilization was facilitated by sonication. The catalyst / anthracene solution was passed through a tared 0.2 μm PTFE membrane filter (PALL Acrodisc CR 25 mm). To determine the mass of the insoluble material, the membrane filter was dried under high vacuum. The filtered solution was placed in an NMR tube (0.9 mL for C6D6 and 0.8 mL for CD2Cl2) in air, capped, and allowed to stand at ambient temperature. From these samples, 1 1 H NMR spectra were obtained. 1 H-NMR spectroscopy: 1 H NMR spectra were collected using a Varian spectrometer operating at 400 MHz. Spectra were collected at ambient temperature and contained residual amounts of deuterated solvent.1 H signal: δ (parts per million) was reported relative to dichloromethane 5.32 and benzene 7.16. 1 The H pulse was 5.95 μs, the acquisition time was 2.55 s, and the relaxation wait time was 1.0 s. 1 For each H spectrum, 16 transients were collected. 1 H NMR FID data were apodized at 1 Hz and then Fourier transformed (real part 32K + imaginary part). The relative amount of ruthenium catalyst retaining cis- or trans-chloride was determined by integrating the signal from the 2-position of 3-phenylindenylidene. The total ruthenium catalyst in solution was determined by summing the integrals of the cis- and trans-chlorides at the 2-position of 3-phenylindenylidene compared to the integral of the 9- and 10-position (2H) signals of the internal anthracene standard. result Solubility. Anthracene was completely soluble in CD2Cl2 and C6D6. trans-C947 and cis-C947 were almost completely soluble in CD2Cl2, but cis-C947 was less soluble than trans-C947 in C6D6 (Table 1). It was not possible to completely remove residual solvent from the PTFE membrane filters. Also, some of the measured residual mass in Table 1 is the result of evaporation of this residual solvent. [Table 2] The signal from the 2-position of trans-C947 in C6D6, 3-phenylindenylidene, is a doublet at δ 8.79 (d, J = 7.6 Hz, 1H). This signal was integrated and compared with the signal of anthracene at δ 8.15 (s, 2H). No new doublet representing cis-C947 was detected during the experiment (Figure 2). The signal from the 2-position of cis-C947 in C6D6, 3-phenylindenylidene, is a doublet at δ 9.94 (d, J = 7.4 Hz, 1H). This signal was integrated and compared with the signal from anthracene at δ 8.15 (s, 2H). As the experiment progressed, a new doublet, representing trans-C947, appeared at δ 8.79 (d, J = 7.4 Hz, 1H) (Figure 2). The signal from the 2-position of trans-C947 in CD2Cl2, 3-phenylindenylidene, is a doublet at δ 8.18 (d, J = 7.5 Hz, 1H). This signal was integrated and compared with the signal from anthracene at δ 8.45 (s, 2H). As the experiment progressed, a new doublet representing cis-C947 gradually appeared at δ 9.00 (d, J = 7.5 Hz, 1H) (Figure 2). The signal from the 2-position of cis-C947 in CD2Cl2, 3-phenylindenylidene, is a doublet at δ 9.00 (d, J = 7.5 Hz, 1H). This signal was integrated and compared with the signal from anthracene at δ 8.15 (s, 2H). As the experiment progressed, a new doublet, representing trans-C947, appeared at δ 8.17 (d, J = 7.5 Hz, 1H) (Figure 2).

[0220] Example 14 [ka]

[0221] trans-RuCl2(sIMes)(phenylindenylidene) (Ph2P(Op-C6H4OMe)), trans-C977: To a round-bottom flask containing a magnetic stir bar, under N2, was placed trans-C748·2Py (9.06 g, 10 mmol), to which degassed CHCl2 (100 mL) was added. Phosphite Ph2P(Op-PhOMe) (3.39 g, 11 mmol) was added via syringe. The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 15 min. The solvent was removed under high vacuum. Degassed toluene (100 mL) was added, and the solvent was removed under high vacuum. A second addition of degassed toluene (100 mL) was performed, and the solvent was removed under high vacuum. Attempts to recrystallize the resulting crude material in CHCl (50 mL) / heptane (50 mL) produced a black oil. The supernatant was decanted and the oil was treated with EtOAc (50 mL) / heptane (50 mL) to give a black solid powder. This solid was collected, dissolved in CHCl (500 mL), and passed through a silica gel plug (D×H: 2"×2"). The silica gel plug was washed with CHCl (500 mL). The CHCl eluate and washings were combined and concentrated under high vacuum. Attempts to recrystallize the crude residue from CHCl / heptane produced a black oil. The supernatant was discarded, and the oil was placed under high vacuum to give a black foamy solid. Yield: 5.1 g. 1 H NMR (400MHz, CDCl3, ppm): δ8.13(d,J=8Hz,1H),7.55(m,2H),7.48(m,1H),7. 34(m,2H),7.25-7.10(m,7H),7.06-6.92(m,8H),6.71(s,1H),6.41(m,3H),6. 24(m,2H),6.05(s,1H),4.12-4.04(m,2H),3.94-3.80(m,2H),3.47(s,3H),2 .66(s,3H),2.64(s,3H),2.38(s,3H),2.23(s,3H),1.99(s,3H),1.78(s,3H). 31 P NMR (161.8MHz, CDCl3, ppm): δ127.30(s).

[0222] Example 15 [ka]

[0223] cis-RuCl(sIMes)(phenylindenylidene) (PhP(Op-CHOMe)), cis-C977: The foamy solid (trans-C977, 5.0 g) was dissolved in DCM (500 mL) and passed through a silica gel plug (D×H: 3"×2"). The plug was washed with CHCl. ​​The first light red fraction (trans-C977) was discarded, and the second dark brown fraction was retained. The eluent was changed to EtOAc, and the third fraction was collected. The second and third fractions were combined, and the solvent was removed under high vacuum. Methanol was added to wash the solid, and the slurry was filtered. The solid was collected and further crystallized from CHCl / methanol to give cis-C977 as a pale purple solid. Yield: 2.3 g. 1 H NMR (400MHz, CDCl3, ppm): δ9.10(d,J=7Hz,1H),7.57-7.53(m,2H),7.49-7.45(m,1H),7.37-7. 32(m,4H),7.30-7.27(m,1H),7.23-7.19(m,2H),7.11-7.04(m,3H),6.89-6.87(m,1H),6.82(br s,1H),6.68-6.65(m,4H),6.53-6.51(m,2H),6.29-6.26(m,4H),6.23(s,1H),6.08(s,1H),3.98-3.95(m ,1H),3.75-3.68(m,6H),2.77(s,3H),2.65(s,3H),2.30(s,3H),2.13(s,3H),2.00(s,3H),1.58(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ136.97(s).

[0224] Example 16 [ka]

[0225] trans-RuCl(sIMes)(phenylindenylidene) (PhP(Oi-Pr)), trans-C913: To a round-bottom flask containing a magnetic stir bar and under N2, trans-C748·2Py (25 g, 27.6 mmol) was added degassed heptane (400 mL). Phosphite PhP(Oi-Pr) (7.4 g, 30.4 mmol) was added via syringe. The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 1 h. Additional phosphinite PhP(Oi-Pr) (2.0 g, 8 mmol) was added. The reaction was stirred at ambient temperature (20-25 °C) for 16 h. The slurry was filtered and washed with heptane. The solid was dissolved in degassed CHCl (250 mL) and the solvent was reduced under high vacuum at ambient temperature using a water bath. Heptane (100 mL) was added, followed by solvent reduction under high vacuum. A black oil formed at the bottom of the flask. The supernatant was removed, and CHCl (100 mL) was added to the black oil, and the solvent was reduced under high vacuum. Heptane (50 mL) was added again, resulting in a black oil at the bottom of the flask. The supernatant was removed, and the black oil was dissolved in degassed CHCl (200 mL). This solution was filtered through a silica plug (D×H: 2"×1") using CHCl as the eluent. The first fraction was concentrated to dryness. The resulting solid was crushed and sieved to give the trans isomer as a dark red solid (15.7 g). 1 H NMR(400MHz, CDCl3, ppm): δ7.94(d,J=8Hz,1H),7.60-7.53(m,2H),7.49(m ,1H),7.35(m,2H),7.23-6.90(m,15H),6.59(s,1H),6.40(s,1H),6.04(s, 1H),4.17-4.02(m,3H),3.91-3.75(m,2H),2.71(s,6H),2.04(s,3H),2.16 (s,3H),2.02(s,3H),1.82(s,3H),0.91(d,J=6Hz,3H),0.83(d,J=6Hz,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ115.28(s).

[0226] Example 17 [ka]

[0227] cis-RuCl2(sIMes)(phenylindenylidene) (Ph2P(Oi-Pr)), cis-C913: To a round-bottom flask containing a magnetic stir bar under nitrogen was added degassed methanol (250 mL) containing trans-C913 (2.0 g). The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 16 h. The solvent was removed under high vacuum. The crude solid was dissolved in CHCl2 and filtered through a silica plug (DxH: 4" x 3"). The first fraction was eluted with CHCl2, and the second fraction was eluted with EtOAc. The second fraction was concentrated to dryness, and the resulting solid was washed with methanol (2 x 100 mL). A dark brown crystalline material formed, which was filtered and dried to give the cis isomer. Yield: 0.7 g. 1 H NMR (400MHz, CDCl3, ppm): δ9.02(d,J=7Hz,1H),7.57-7.55(m,2H),7.49(m,2H),7.44-7.36(m,2H),7.35 -7.28(m,4H),7.12-7.06(m,2H),7.02-6.98(m,1H),6.92-6.85(m,1H),6.72-6.67(m,3H),6.64-6.58(m ,3H),6.51(s,1H),6.22(s,2H),4.56-4.49(m,1H),3.98-3.93(m,1H),3.74-3.60(m,3H),2.70(s,3H),2 .60(s,3H),2.57(s,3H),2.10(s,3H),1.96(s,3H),1.69(s,3H),1.48(d,J=6Hz,3H),0.62(d,J=6Hz,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ129.24(s).

[0228] Example 18 [ka]

[0229] trans-RuCl(sIMes)(phenylindenylidene) (PhP(OMe)), trans-C834: To a round-bottom flask containing a magnetic stir bar under nitrogen was placed trans-C748·2Py (20 g, 22 mmol) and degassed heptane (400 mL). The phosphonite ester PhP(OMe)2 (4.1 g, 24.2 mmol) was added via syringe. The reaction vessel was evacuated and refilled with N2 (3x). The slurry was stirred under N2 at ambient temperature (20–25 °C) for 1 h. The slurry was filtered, and the resulting solid was recrystallized from CHCl2 and heptane to give a purple solid (15.8 g). 1 H NMR (400MHz, CDCl3, ppm): δ8.19(d,J=8Hz,1H),7.62-7.59(m,2H),7.49-7.47(m,1H),7 .38-7.34(m,2H),7.20-7.13(m,4H),7.05-7.00(m,3H),6.98-6.96(m,1H),6.89(s,1H), 6.85(s,1H),6.75(s,1H),6.42(s,1H),6.07(s,1H),4.12-4.06(m,2H),3.87-3.81(m,2 H),3.23-3.12(m,6H),2.65(s,6H),2.25(s,3H),2.22(s,3H),1.98(s,3H),1.77(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ148.60(s).

[0230] Example 19 [ka]

[0231] trans-RuCl(sIMes)(phenylindenylidene) (PhP(OPh)), trans-C963: In a round-bottom flask containing a magnetic stir bar, trans-C748·2Py (20.0 g, 22.1 mmol) was dissolved in toluene (25 mL) sparged with N2. Diphenyl phenylphosphinite ((OPh)2PhP, 7.15 g, 24.3 mmol, 1.1 equiv.) was added via syringe. The reaction vessel was evacuated and refilled with N2 (3x). The reaction was stirred under N2 at ambient temperature for 1 h. The solvent was removed from the reaction under high vacuum. To the reaction was added 50 mL of CHCl2. The flask was stirred briefly, and the solvent was removed under reduced pressure. The resulting solid was dried under high vacuum over the weekend. The solid was suspended in CHCl2 and MeOH, stirred briefly, and the solvent was removed under reduced pressure. The resulting residue was dissolved in CHCl and applied to a silica plug. Elution was performed by adding CHCl until colorless. The CHCl solution was concentrated under reduced pressure, and hexane was added. Further concentration gave a slurry, which was filtered and washed with hexane. The dark brown solid was dried under high vacuum overnight to give 15.51 g (73%). 1 H NMR(400MHz,CDCl3)δ8.28(dd,J=7.4,1.2Hz,1H),7.72-7.66(m,2H),7.61-7.57(m,2H),7.49(tt,J=7.5, 1.2Hz,1H),7.41-7.31(m,3H),7.25-7.17(m,2H),7.12(td,J=7.4,1.3Hz,1H),7.05(td,J=7.5,1.2Hz,1H ),6.98-6.77(m,9H),6.75(s,1H),6.69(s,1H),6.67-6.56(m,3H),6.35(s,1H),6.06(s,1H),4.08-3.91( m,2H),3.90-3.70(m,2H),2.57(s,3H),2.54(s,3H),2.26(s,3H),2.17(s,3H),1.96(s,3H),1.74(s,3H). 31 P NMR (162MHz, CDCl3) δ151.47.

[0232] Example 20 [ka]

[0233] cis-RuCl(sIMes)(t-butylvinylidene) (PhP(OMe)), cis-C777: To a round-bottom flask containing a magnetic stir bar under nitrogen was added trans-C719v (5.0 g, 7.0 mmol) and degassed CHCl (40 mL). Phosphite PhP(OMe) (2.26 g, 10.5 mmol) was added via syringe. The reaction vessel was evacuated and backfilled with N (3x). The reaction was stirred under N at ambient temperature (20-25 °C) for 60 min to give a yellow crystalline solid. The crude material was filtered, washed with heptane, and dried under high vacuum to give a crude yellow solid (3.6 g). The crude yellow solid (1.6 g) was dissolved in degassed CHCl (200 mL) and filtered through Celite. The filtrate was concentrated under high vacuum and the resulting solid was recrystallized from CH2Cl2 / heptane. The crystals were filtered, washed with heptane, and dried under high vacuum to give a yellow solid. Yield: 1.3 g. 1 H NMR(400MHz,CD2Cl2,ppm):δ7.46-7.41(m,1H),7.39-7.28(m,5H),7.18-7.14(m,3H),7.00(s,1H),6.95(s,1H),6.90-6.85(m,2H),6.64(s,1 H),4.06-3.85(m,4H),3.35(d,J=11Hz,3H),2.80(s,3H),2.77(s,3H)2 .40(s,6H),2.33(s,3H),2.09(s,3H),1.93(d,J=5Hz,1H),0.33(s,9H). 31 P NMR (161.8MHz, C6D6, ppm): δ135.15(s).

[0234] Example 21 [ka]

[0235] cis-RuCl(sIMes)(t-butylvinylidene) (PhP(Oi-Pr)), cis-C805v: To a round-bottom flask containing a magnetic stir bar under N2, trans-C719v (5.0 g, 7.0 mmol) was added degassed and dried toluene (30 mL). Phosphite PhP(Oi-Pr) (1.9 g, 7.7 mmol) was added via syringe. The reaction vessel was evacuated and refilled with N2 (3x). The solid did not dissolve, so degassed CHCl2 (10 mL) was added. The reaction was stirred under N2 at ambient temperature (20-25 °C) for 60 min to give a fluffy solid. The crude material was filtered, washed with heptane, and dried under high vacuum to give a crude solid. The filtrate was concentrated under high vacuum to give a solid, which was washed with heptane. The combined crude solids were treated with degassed CHCl (20 mL), and the reaction vessel was evacuated and backfilled with N (3x). Some additional PPh(Oi-Pr) (0.8 g) was added, and the reaction was stirred under N at ambient temperature (20-25 °C) for 60 min. The material was concentrated under high vacuum, and the resulting crude product was recrystallized from CHCl / heptane to give a powder. This powder was then recrystallized from CHCl / methanol to give a microcrystalline solid. Yield: 3.5 g. 1 H NMR (400MHz, CDCl3, ppm): δ7.58-7.53(m,2H),7.34-7.26(m,4H),7.12(s,1H),7.08- 7.06(m,2H),6.95(s,2H),6.92-6.79(m,2H),6.65(s,1H),4.26-4.22(m,1H),4.12-4 .06(m,1H),4.01-3.93(m,2H),3.81-3.76(m,1H),2.85(s,3H),2.81(s,3H),2.39-2. 34(m,12H),1.95(d,J=5Hz,1H),1.27(d,J=6Hz,3H),0.52(d,J=6Hz,3H),0.39(s,9H). 31 P NMR (161.8MHz, C6D6, ppm): δ130.17(s).

[0236] Example 22 [ka]

[0237] trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(Oi-Pr)), trans-C791: In an argon-filled glovebox, a 40 mL scintillation vial equipped with a magnetic stir bar was charged with C705 (2.00 g, 2.84 mmol) and dichloromethane (15 mL). To this stirred solution was added the phosphinite PhP(Oi-Pr) (0.693 g, 2.84 mmol) in dichloromethane (5 mL). The reaction was stirred at room temperature for 1 h, and then the volatiles were removed. The resulting residue was recrystallized from dichloromethane / pentane at room temperature to give trans-C791 (1.49 g, 66.1%, purity >95%). 1 H NMR(400MHz,CD2Cl2,ppm):δ18.43(d,J=11.2Hz,1H),7.30-7.08(m,10H),6.90(s,2H),6.84-6.79(m,1H),6.77(s,2H),4.04-3.8 5(m,4H),3.83-3.71(m,1H),2.56(s,6H),2.35(s,6H),2.32(s,3H),2.23(s,3H),1.12(s,3H),0.98(s,3H),0.95(d,J=6.0Hz,6H). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ126.6(s).

[0238] Example 23 [ka]

[0239] trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OMe)), trans-C763: In an argon-filled glovebox, C705 (2.00 g, 2.84 mmol) and dichloromethane (15 mL) were placed in a 40 mL scintillation vial equipped with a magnetic stir bar. To this stirred solution was added the phosphinite PhP(OMe) (0.556 mL, 2.84 mmol) in dichloromethane (5 mL). The reaction was stirred at room temperature for 1 h, and then the volatiles were removed. The resulting residue was recrystallized from dichloromethane / pentane at room temperature to give trans-C763 (1.35 g, 62.2%, purity >95%). 1 H NMR(400MHz,CD2Cl2,ppm):δ18.37(d,J=11.2Hz,1H),7.36-7.29(m,2H),7.27-7.15(m,8H),7.06-7.00(m,1H),6.88(s,2H),6.79 (s,2H),4.13-3.87(m,4H),3.15(d,J=12.8Hz,3H),2.56(s,6H),2.37(s,6H),2.32(s,3H),2.24(s,3H),1.10(s,3H),1.03(s,3H). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ134.4(s).

[0240] Example 24 [ka]

[0241] trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OEt)), trans-C777: In an argon-filled glovebox, C705 (2.00 g, 2.84 mmol) and dichloromethane (15 mL) were placed in a 40 mL scintillation vial equipped with a magnetic stir bar. To this stirred solution was added the phosphinite PhP(OEt) (0.607 mL, 2.84 mmol) in dichloromethane (5 mL). The reaction was stirred at room temperature for 1 h, and then the volatiles were removed. The resulting residue was recrystallized from toluene / pentane at −35 °C to give trans-C777 (1.48 g, 67.2%, purity >95%). 1 H NMR(400MHz,CD2Cl2,ppm):δ18.39(d,J=11.2Hz,1H),7.34-7.26(m,2H),7.24-7.14( m,8H),7.03-6.95(m,1H),6.89(s,2H),6.79(s,2H),4.08-3.88(m,4H),3.36(pseudo) pentet,J=6.9Hz,2H),2.56(s,6H),2.36(s,6H),2.32(s,3H),2.24(s,3H),1.11(s,3H),1.07(t,J=6.9Hz,3H),1.03(s,3H). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ129.8(s).

[0242] Example 25 [ka]

[0243] trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OMe)), trans-C717: To a round-bottom flask containing a magnetic stir bar under nitrogen was added trans-C705 (28.7 g, 40.1 mmol) and degassed CHCl (500 mL). The phosphonite PhP(OMe) (10.3 g, 61 mmol) was added. The reaction vessel was evacuated and backfilled with N (3x). The reaction was stirred under N at ambient temperature (20-25 °C) for 60 min. The solvent was removed under high vacuum to give a crude solid. This crude solid was dissolved in CHCl (50 mL) and passed through a silica gel plug (D x H: 2" x 1"). The product fraction was eluted with CHCl (200 mL). Heptane (200 mL) was added and the solution was concentrated to give a black oil. EtOAc was added to the black oil to give a yellow solid. This was filtered and washed with heptane to give a beige solid (9.19 g). The solid was recrystallized from CH2Cl2 (25 mL), EtOAc (50 mL), and heptane (50 mL) to give 6.19 g of product. 1 H NMR (400MHz, CDCl3, ppm): δ18.19 (dd, J=12Hz and 1Hz, 1H), 7.30-7.17 (m, 5H), 7.02-6.99 (m, 1H), 6.80 (s, 2H), 6.70 (s, 2H), 4.06-4. 00(m,2H),3.87-3.93(m,2H),3.19(d,J=12Hz,6H),2.56(s,6H),2.32(s,6H),2.21(s,3H),2.18(s,3H),1.02(s,3H),0.97(s,3H). 31 P NMR (161.8MHz, C6D6, ppm): δ160.00(s).

[0244] Example 26 [ka]

[0245] trans-RuCl(sIMes)(3-methyl-2-butenylidene) (PhP(OPh)), trans-C825: To a round-bottom flask containing a magnetic stir bar under N2, trans-C705 (70.5 g, 100 mmol) was added degassed CHCl2 (500 mL). Phosphite PhP(OPh) (30.58 g, 110 mmol) was added. The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 1 h. The solvent was removed under high vacuum, and degassed toluene (500 mL) was added. The reaction vessel was evacuated and backfilled with N2 (3x). The reaction was stirred under N2 at ambient temperature (20-25 °C) for 1 h. The solvent was removed under high vacuum, and degassed toluene (500 mL) was added. The solid particles in the solution were filtered off, and the solvent of the filtrate was removed under high vacuum to give a solid residue. Degassed methanol (500 mL) was then added to wash the solid, which was then filtered and washed with methanol. The solid was then dissolved in CHCl, and additional phosphinite (1.0 g, 3.6 mmol) was added. The solution was concentrated, and degassed heptane (250 mL) was added. The solvent was then reduced, and the flask was stored in the freezer for 16 hours. A solid formed, which was filtered and washed with heptane. The solid was dissolved in CHCl (100 mL), and the solution was passed through a silica gel plug (D×H: 3"×2"). The filtrate was concentrated to dryness on a rotary evaporator. The solid was dissolved in degassed CHCl (250 mL) and reduced to approximately 100 mL. Heptane (500 mL) was slowly added dropwise to the solution using a dropping funnel. A solid precipitated and was filtered. The filtrate was washed with heptane and dried under high vacuum. The crude solid was dissolved in CH2Cl2 (40 mL) and heptane (500 mL) was added slowly again via a dropping funnel. The solid formed again was filtered and washed with heptane to give the product. Yield: 6.2 g. 1H NMR(400MHz,CD2Cl2,ppm):δ18.29(d,J=11.2Hz,1H),7.35-7.30(m,5H),7 .23-7.18(m,4H),7.16-7.12(m,1H),6.97-6.93(m,2H),6.85-6.80(m,3H) ,6.75(s,2H),6.59-6.56(m,2H),4.03-3.97(m,2H),3.92-3.87(m,2H),2. 50(s,6H),2.3(s,6H),2.31(s,3H),2.21(s,3H),1.02(s,3H),1.00(s,3H). 31 P NMR (161.8MHz, CD2Cl2, ppm): δ137.11(s).

[0246] Catalytic activity of the complex Examples 27(a)-(x).

[0247] The catalytic activity of the complexes was evaluated in ring-opening metathesis polymerization (ROMP) reactions as follows: A 250 mL beaker was charged with 100 g of DCPD-HT monomer. The monomer was equilibrated to the desired temperature in an oil bath (30°C ± 0.5°C). A J-type thermocouple was suspended directly over the center of the monomer. The test catalyst was dissolved in a solvent (either toluene or CHCl) to form a catalyst solution. This catalyst solution was then added to the monomer at a molar ratio of 45,000:1 (monomer:catalyst) to obtain the ROMP composition. The addition of the catalyst to the monomer to obtain the ROMP composition marked the start of the ROMP reaction; therefore, this was designated time zero. Temperature readings were recorded using a thermocouple. The exotherm time was determined by measuring the amount of time (i.e., the time difference) elapsed between time zero and the time when a propagating interface of the ROMP composition was first visually observed as it transitioned from a liquid or gel state to a cured polymer state. The ROMP reaction was stopped 2 hours after adding the catalyst solution to the monomer. The time to exotherm is expressed as follows: slow: over 120 minutes, moderately slow: 30-120 minutes, moderate: 1-30 minutes, and fast: less than 1 minute. The peak exotherm temperatures are shown in Table 2. [Table 3]

[0248] Surprisingly, the trans and cis catalysts of the present invention exhibit different exothermic times under ROMP conditions. For phenylindenylidene systems, the trans catalyst exhibits faster kinetics than the cis catalyst, and similarly, for benzylidene systems, the trans catalyst exhibits faster kinetics than the cis catalyst. The same trend is observed between the trans and cis phosphinite and phosphonite catalyst systems.

[0249] To successfully mold an article, it is important to be able to control the rate of polymerization of the ROMP composition. In a typical molding scenario, after catalysis, the ROMP composition increases in viscosity and progresses from a liquid state through a gel state, undergoing an exothermic event to produce the final polymer. In particular, the ROMP composition must not exotherm (i.e., cure) before filling the mold. The time required for mold filling can vary from less than a minute to several minutes to several hours. The ability to select from a wide variety of catalysts that provide different exotherm time ranges is advantageous for both molding techniques and for manufacturing articles.

Claims

1. Formula (V): 【Chemistry 1】 [In the formula, Q is a group having the structure -CR １１ R １２ -CR １３ R １４ -or-CR １１ =CR １３ - (wherein, R １１ , R １２ , R １３ and R １４ are two atom bonds having independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or a functional group; R ３ and R ４ may be unsubstituted phenyl or phenyl substituted with one or more substituents; X １ and X ２ are independently halogen and are bonded to Ru in a trans configuration; L ２ is P(Ph) ２ (OPh), P(Ph) ２ (OC ６ H ４ -p-OMe), P(Ph) ２ (O-iPr), P(Ph) ２ (OEt), and P(Ph)(OMe) ２ is a group selected from the group consisting of m is 0, 1 or 2; R １ and R ２ are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or R １ and R ２ may be joined together to form a ring, which may be substituted or unsubstituted. A metal carbene olefin metathesis catalyst represented by the structure:

2. In formula (V), m is 0 and R １ and R ２ 2. The metal carbene olefin metathesis catalyst of claim 1, wherein are linked together to form a phenylindenylidene group.

3. R ３ and R ４ is unsubstituted phenyl or C １ ~C ２０ Alkyl, substituted C １ ~C ２０ Alkyl, C １ ~C ２０ Heteroalkyl, substituted C １ ~C ２０ Heteroalkyl, C ５ ~C ２４ Aryl, substituted C ５ ~C ２４ Aryl, C ５ ~C ２４ Heteroaryl, C ６ ~C ２４ Aralkyl, C ６ ~C ２４ 10. The metal carbene olefin metathesis catalyst of claim 1, which is a phenyl substituted with one or more of the following substituents: alkaryl or halide.

4. m is 0, Q is a group having the structure -CR １１ R １２ -CR １３ R １４ - (wherein, R １１ , R １２ , R １３ and R １４ are independently hydrogen), R ３ and R ４ is phenyl, each substituted with up to three substituents selected from methyl or isopropyl; X １ and X ２ is Cl, L ２ But P(Ph) ２ (OPh), P(Ph) ２ (OC ６ H ４ -p-OMe), P(Ph) ２ (O-iPr), P(Ph) ２ (OEt), and P(Ph)(OMe) ２ is a group selected from the group consisting of R １ is hydrogen, and R ２ But C １ ~C ６ Alkyl or C １ ~C ６ phenyl, vinyl, optionally substituted with one or more moieties selected from alkoxy; １ and R ２ may be linked together to form a phenylindenylidene.

5. 10. A ROMP (ring-opening metathesis polymerization) composition comprising at least one resin composition and at least one metal carbene olefin metathesis catalyst according to claim 1, wherein the resin composition comprises at least one cyclic olefin.

6. 6. The ROMP (ring-opening metathesis polymerization) composition of claim 5, wherein said at least one cyclic olefin is a norbornene derivative.

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