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  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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  • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• This invention relates generally to olefin metathesis catalysts, and more particularly pertains to new Group 8 transition metal complexes that are useful as latent olefin metathesis catalysts.
• the invention has utility in the fields of catalysis, organic synthesis, and organometallic chemistry.
• Olefin metathesis catalysis is a powerful technology, which in recent years has received tremendous attention as a versatile method for the formation of carbon-carbon bonds and has numerous applications in organic synthesis and polymer chemistry (R.H. Grubbs, Handbook of Metathesis, Vol. 2 and 3; Wiley NCH, Weinheim, 2003).
• the family of olefin metathesis reactions includes ring-closing metathesis (RCM), cross metathesis (CM), ring- opening metathesis polymerization (ROMP), and acyclic diene metathesis polymerization (ADMET).
• olefin metathesis stems from the development of several well- defined transition metal complexes, such as the Schrock molybdenum catalysts and the Grubbs ruthenium and osmium catalysts (see, e.g., Schrock (1999) Tetrahedron 55, 8141- 8153; Schrock (1990) Ace. Chem. Res. 23, 158-165; Grubbs et al. (1998) Tetrahedron 54, 4413-4450; Trnka et al. (2001) Ace. Chem. Res. 34, 18-29; Grubbs, Handbook of Metathesis, Vol. 1; Wiley NCH, Weinheim, 2003).
• transition metal complexes such as the Schrock molybdenum catalysts and the Grubbs ruthenium and osmium catalysts
• M is ruthenium (Ru) or osmium (Os)
• X represents a halogen (e.g., CI, Br, or I)
• R represents an alkyl, cycloalkyl, or aryl group (e.g., butyl, cyclohexyl, or phenyl)
• a different strategy to tune olefin metathesis catalysts involves linking two of the ligands that are attached to the metal center.
• chelating carbene species reported by Hoveyda and others (Gaber et al. (2000) J. Am. Chem. Soc. 122, 8168- 8179; Kingsbury et al. (1999) J. Am. Chem. Soc. 121, 791-799; Harrity et al. (1997) J. Am. Chem. Soc. 119, 1488-1489; Harrity et al. (1998) J. Am. Chem. Soc. 120, 2343-2351). These catalysts are exceptionally stable and can be purified by column chromatography in air.
• Catalyst PR-1 and PR-2 Representative such catalysts, designated Catalyst PR-1 and PR-2, are illustrated in FIG. 1.
• Catalyst PR-2 combines excellent stability and enhanced activity, and actively promotes the cross-metathesis of acrylonitrile and terminal olefins in moderate to excellent yields.
• While most of these efforts have focused on increasing the activity and initiation rate of the ruthenium carbene metathesis catalysts, there remains a need for highly active catalysts that initiate more slowly (i.e., are more latent). This can be a particularly beneficial feature when performing metathesis polymerizations, which, in practice, typically require a significant period of time (the "work-time") within which to mix, handle, and process the catalyst resin mixture before it gels or solidifies.
• PR 3 )(Cl) 2 Ru(CH(CH 2 ) 2 -C,N-2-C 5 H 4 N 2-pyridylethanyl ruthenium carbene complex
• 2-(3-butenyI)pyridine 2-(3-butenyI)pyridine developed by van der Schaaf (van der Schaaf et al. (2000) J. Organometallic Chemistry 606, 65-74).
• Patent Number 6,306,987 teaches that phosphine-ligated bridging carbene complexes of the general structure D are latent metathesis catalysts, whereas similar NHC-ligated complexes of the general structure E are not (e.g., Courchay et al. (2003) Macromolecules 36, 8231-8239). These observations suggest that it is difficult to achieve latency with the high- activity catalysts comprising NHC ligands.
• the present invention relates to novel high-activity but latent olefin metathesis catalysts that comprise an NHC ligand and a chelating carbene ligand.
• catalysts are provided that have a latency period on the order of minutes to hours, or even longer. It has also been surprisingly discovered that the initiation rate of some of these catalysts can be substantially varied via simple isomerization of the complexes and that the reactivity can be tuned over a wide range by controlling the ratio of the different isomers.
• the catalysts are particularly useful in the RCM of acyclic olefins and the ROMP of cyclic olefins.
• the present catalytic complexes generally have the structure of formula (I)
• bonds indicated as dashed lines and designated as ⁇ and ⁇ represent single bonds or unsaturated (e.g., double) bonds, with the proviso that ⁇ and ⁇ cannot both be unsaturated bonds;
• M is a Group 8 transition metal, generally ruthenium (Ru) or osmium (Os);
• R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
• Q is an organic diradical, i.e., a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group;
• X and X are anionic ligands, and may be the same or different;
• L 1 is a neutral electron donor ligand, and p is zero or 1;
• L 2 is selected from NR 7 and PR 7 , where R 7 is as defined previously;
• Y and Z are linkages independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, -O-, -S-, -NR 9 -, and -PR 9 -, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom- containing hydrocarbyl, and further wherein Y and Z, or L 2 and Z, may represent adjacent atoms in an aromatic ring; [00025] m is zero or 1; and [00026] n is zero or 1, [00027] and also include isomers thereof.
• FIG. 1 provides the molecular structures of two metathesis catalysts of the prior art, indicated as Pr-1 and Pr-2.
• FIG. 2 provides the molecular structures of two representative catalytic complexes of the invention, indicated as Catalysts 2a and 2b.
• FIG. 3 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2a.
• FIG. 4 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2b.
• FIG. 5 provides the molecular structures of two representative catalytic complexes of the invention, indicated as Catalysts 4 and 5.
• FIG. 6 provides the molecular structures of additional representative catalytic complexes of the invention.
• FIG. 7 schematically depicts a method for synthesizing representative catalytic complexes 2a, 4 and 5 of the invention.
• FIG. 8 schematically depicts a method for synthesizing representative catalytic complexes 2b of the invention.
• FIG. 9 provides the molecular structure of additional representative catalytic complexes of the invention.
• FIG. 10 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 1, 2a, 2b and 12, as described in Example 15.
• FIG. 11 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 2a, 4 and 5, as described in Examplel6.
• FIG. 12 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 2a, 7 and 8, as described in Example 17.
• FIG. 13 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 7, 8, 9, 10, and 11, as also described in Example 17.
• FIG. 14 provides the exotherms for the RCM reaction of diethyldiallyl malonate to assess the activity of catalysts 6 and 8, as described in Example 18.
• FIG. 15 provides the exotherms for the ROMP reaction catalyzed by catalysts 2a and 2b, as described in Example 19.
• FIG. 16 provides the exotherms for the ROMP reaction catalyzed by catalysts 2a, 2b and 12, as also described in Example 19.
• FIG. 17 provides the exothenns for the ROMP reactions catalyzed using different mixtures of 2a and 2b, as described in Example 20.
• FIG. 18 provides the exotherms for the ROMP reaction catalyzed by catalysts 2a, 7 and 8, as described in Example 21.
• alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 20 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, »-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms.
• lower alkyl intends an alkyl group of 1 to 6 carbon atoms
• cycloalkyl intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms.
• substituted alkyl refers to alkyl substituted with one or more substituent groups
• heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom.
• alkyl and lower alkyl include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
• alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.
• alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 20 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, rc-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
• Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
• lower alkenyl intends an alkenyl group of 2 to 6 carbon atoms
• specific term “cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms.
• substituted alkenyl refers to alkenyl substituted with one or more substituent groups
• heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
• alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
• alkynyl refers to a linear or branched hydrocarbon group of 2 to about 20 carbon atoms containing at least one triple bond, such as ethynyl, n- propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms.
• substituted alkynyl refers to alkynyl substituted with one or more substituent groups
• heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
• alkynyl and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
• alkynylene refers to a difunctional alkynyl group, where "alkynyl” is as defined above.
• alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as -O-alkyl where alkyl is as defined above.
• a "lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
• alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
• alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
• aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
• Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms.
• Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
• Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
• heteroatom-containing aryl and “heteroaryl” refer to aryl substituent, in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.
• aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl” is as defined above.
• An "aryloxy” group may be represented as -O-aryl where aryl is as defined above.
• Preferred aryloxy groups contain 5 to 20 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms.
• aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo- phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
• alkaryl refers to an aryl group with an alkyl substituent
• aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
• Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
• Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-l,4-diene, and the like.
• aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl- propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4- phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.
• alkaryloxy and aralkyloxy refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.
• acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, or -(CO)-aralkyl
• acyloxy refers to substituents having the formula -O(CO)- alkyl, -O(CO)-aryl, or -O(CO)-aralkyl, wherein "alkyl,” “aryl, and “aralkyl” are as defined above.
• cyclic refers to alicyclic or aromatic substituents that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
• alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.
• halo and halogen are used in the conventional sense to refer to a chloro, bromo, and fluoro or iodo substituent.
• Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
• lower hydrocarbyl intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
• hydrocarbylene intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
• lower hydrocarbylene intends a hydrocarbylene group of 1 to 6 carbon atoms.
• Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
• heteroatom-containing hydrocarbyl and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom
• substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
• heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
• the te ⁇ n "hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
• heteroatom-containing refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
• heteroalkyl refers to an alkyl substituent that is heteroatom-containing
• heterocyclic refers to a cyclic substituent that is heteroatom-containing
• heteroaryl and heteroaromatic respectively refer to "aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
• a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.”
• substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
• substituents include, without limitation: functional groups referred to herein as "Fn,” such as halo, hydroxyl, sulfhydryl, -C2 0 alkoxy, C2-C20 alkenyloxy, C 2 -C 20 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, acyl (including C 2 -C 2 o alkylcarbonyl (-CO- alkyl) and C 6 -C 24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C20 alkyl- carbonyloxy (-O-CO-alkyl) and C 6 -C 24 arylcarbonyloxy (-O-CO-aryl)), C2-C2 0 alkoxycarbonyl (-(CO)-O-alkyl), C 6 -C 24 aryloxycarbonyl (-(CO)
• the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
• the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
• the use of bold and dashed lines to denote particular conformation of groups follows the IUPAC convention. A bond indicated by a broken line indicates that the group in question is below the general plane of the molecule as drawn, and a bond indicated by a bold line indicates that the group at the position in question is above the general plane of the molecule as drawn.
• the invention provides a Group 8 transition metal complex having the structure of formula (I)
• bonds indicated as dashed lines and designated as ⁇ and ⁇ represent single bonds or unsaturated (e.g., double) bonds, with the proviso that ⁇ and ⁇ cannot both be unsaturated bonds;
• M is a Group 8 transition metal
• R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
• Q is an organic diradical, i.e., a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group;
• X 1 and X 2 are anionic ligands, and may be the same or different;
• L 1 is a neutral electron, donor ligand, and p is zero or 1;
• L 2 is selected from NR 7 and PR 7 , where R 7 is as defined previously;
• Y and Z are linkages independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, -O-, -S-, -NR 9 -, and -PR 9 -, wherein R 9 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom- containing hydrocarbyl, and further wherein Y and Z, or L 2 and Z, may represent adjacent atoms in an aromatic ring; [00080] m is zero or 1 ; and [00081] n is zero or 1 , [00082] as well as isomers thereof. [00083] More particularly:
• the metal center designated as M is a Group 8 transition metal, preferably ruthenium or osmium. In a particularly preferred embodiment, M is ruthenium.
• R 1 and R 2 are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C 2 -C 2 o alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted -C20 alkyl, C2-C 20 alkenyl, C2-C2Q alkynyl, C 5 -C2 4 aryl, C 6 -C2 4 alkaryl, C 6 -C 24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C1-C20 alkyl, C2-C20 alkenyl, C
• R 1 and R 2 are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R 1 and R 2 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like.
• R 1 and R 2 are the same and are each unsubstituted phenyl or phenyl substituted with up to> three substituents selected from d-do alkyl, substituted C1-C2Q alkyl, C 1 -C 20 heteroalkyl, substituted -C 20 heteroalkyl, C 5 -C2 4 aryl, substituted C 5 -C2 4 aryl, C -C 24 heteroaryl, C6-C_2 4 aralkyl, C 6 -C 24 alkaryl, and halide.
• any substituents present are hydrogen, C ⁇ -C 12 alkyl, d-C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide. More preferably, R 1 and R 2 are mesityl.
• R and R are independently selected from hydrogen, C ⁇ -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 substituted aryl, d-C 20 functionalized alkyl, C2-C20 functionalized alkenyl, C2-C2 0 functionalized alkynyl, or C 5 -C 4 functionalized substituted aryl where the functional g;roup(s) ("Fn”) may independently be one or more or the following:
• phosphonato (-P(O)(O ⁇ )2), boryl (-BH2), borono (-B(OH)2), or boronato (-B(OR) 2 where R is alkyl or other hydrocarbyl).
• Q is typically selected from hydrocarbylene (e.g., C1-C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylen-e, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), substituted hydrocarbylene (e.g., substituted C ⁇ -C 20 alkylene, C 2 -C 2 o alkenylene, C 2 -C 2 Q alkynylene, C 5 -C2 4 arylene, C 6 -C2 4 alkarylene, or C 6 -C2 4 aralkylene), heteroatom-containing hydrocarbylene (e.g., -do heteroalkylene, C 2 -C 20 heteroalkenylene, C2-C 20 heteroalkynylene, C 5 -C2 heteroarylene, heteroatom-containing C 6 -C 4 aralkylene, or heteroatom-containing C 6 -
• Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage.
• Examples of functional groups here include carboxyl, C1-C20 alkoxy, C 5 -d 4 aryloxy, d-C 2 o alkoxycarbonyl, C 5 -C 24 alkoxycarbonyl, C 2 -C 24 acyloxy, d-C 2 o alkylthio, C 5 -d 4 arylthio, C1-C20 alkylsulfonyl, and d-do alkylsulfinyl, optionally substituted with one or more moieties selected from C ⁇ -C 12 alkyl, C ⁇ -d 2 alkoxy, C 5 -C 14 aryl, hydroxyl, sulfhydryl, formyl, and halide.
• R 3 , R 4 , R 5 , and R 6 are preferably independently selected from hydrogen, C1-C12 alkyl, substituted C ⁇ -C 12 alkyl, Ci-C.s heteroalkyl, substituted d-C 12 heteroalkyl, phenyl, and substituted phenyl.
• any two of R 3 , R 4 , R 5 , and R 6 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C 4 -C 12 alicyclic group or a C 5 or C 6 aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.
• X 1 and X 2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring.
• X 1 and X 2 are each independently hydrogen, halide, or one of the following groups: Ci-do alkyl, C 5 -d- aryl, Ci-do alkoxy, C 5 -C 24 aryloxy, d-do alkoxycarbonyl, C 6 -d 4 aryloxycarbonyl, C2- 4 acyl, C 2 -C 24 acyloxy, C ⁇ -C 20 alkylsulfonato, C 5 -C2 4 arylsulfonato, C ⁇ -C 20 alkylsulfanyl, C 5 -C 24 arylsulfanyl, C 1 -C 20 alkylsulfmyl, C 5 -C 24 arylsulfin
• X 1 and X 2 may be substituted with one or more moieties, if the X 1 and/or X 2 substituent permits, wherein the substituents are typically although not necessarily selected from d-C 12 alkyl, C ⁇ -C 12 alkoxy, C 5 -C 2 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C ⁇ -C 6 alkyl, C . -C 6 alkoxy, and phenyl.
• X and X are halide, benzoate, d-C 6 acyl, -Q alkoxycarbonyl, d-d alkyl, phenoxy, C . -C 6 alkoxy, C ⁇ -C 6 alkylsulfanyl, aryl, or d-C 6 alkylsulfonyl.
• X 1 and X 2 are each halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO,
• X 1 and X 2 are each chloride.
• L 1 is a neutral electron donor ligand which is coordinated to the metal center.
• L 1 may be heterocyclic, in which case it is generally selected from:
• nitrogen-containing heterocycles such as pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1, 2,3 -triazine, pyrrole, 2H- pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, lH-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, b>enzimidazole, bisimidazole, bisimi
• oxygen-containing heterocycles such as 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone,
• mixed heterocycles such as isoxazole, oxazole, thiazole, isothiazole, 1,2,3- oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-
• 1,2,3-dioxazole 3H-l,2-oxathiole, 1,3-oxathiole, 4H-l,2-oxazine, 2H-l,3-oxazine, 1,4- oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.
• L 1 may also be an amine, an imine, a phosphine, an ether, or a thioether.
• L 1 is selected from pyridines, amines, phosphines, imines, ethers, thioethers, furans, and pyrans.
• R 7 and R 8 substituents in this embodiment are C ⁇ -C 12 alkyl or C 5 -C 12 aryl, e.g., methyl, isopropyl, t- butyl, cyclohexyl, and phenyl, and preferred Y groups are -CH 2 -, -CH 2 CH 2 - and substituted analogs thereof .
• Other preferred catalysts, wherein L 2 is PR 7 R 8 have the structure of formula (III)
• R 7 and R 8 substituents are C.-C12 alkyl or C 5 -C 12 aryl, e.g., phenyl, and preferred Y groups are as set forth for complexes of formula (II).
• Particularly preferred catalytic complexes eocompassed by formulae (II) and (III) include, but are not limited to, the following:
• L and Z can be linked through an unsaturated bond, i.e., the dashed line indicating a bond at ⁇ may also represent a double bond or a bond linking adjacent atoms in 9 • 9 * an aromatic ring.
• L is selected from NR 7 and PR 7 , and preferably is NR 7 where R 7 is as defined previously.
• R 7 substituents are C ⁇ -C 12 alkyl or Cs-C 12 aryl, e.g., methyl, isopropyl, t-butyl, cyclohexyl, and phenyl, and preferred Y groups are substituted or unsubstituted methylene or ethylene linkages.
• catalytic complexes encompassed by formulae (IN) and (N) include, but are not limited to, the following:
• Y and Z are linkages independently selected from hydrocarbylene (e.g., d-do alkylene, d-do alkenylene, d-do alkynylene, C 5 -d 4 arylene, C 6 -d 4 alkarylene, or C 6 -d 4 aralkylene), substituted hydrocarbylene (e.g., substituted d-do alkylene, d-do alkenylene, d-do alkynylene, d-d 4 arylene, C 6 -d 4 alkarylene, or C 6 -d 4 aralkylene), heteroatom- containing hydrocarbylene (e.g., d-do heteroalkylene, d-do heteroalkenylene, d-do heteroalkynylene, d-d 4 heteroarylene, heteroatom-containing C 6 -d 4 aralkylene, or heteroatom-containing C 6 -d 4 alkarylene), substituted hydrocar
• Organic diradicals that can serve as Y and/or Z include, by way of example, the following groups: methylene (VI), ethylene (VII), vinylene (NIII), phenylene (IX), cyclohexylene (X), and naphthylenes (XI) and (XII).
• organic diradicals may also serve as the linkage Q.
• M is ruthenium
• Q is 1 9 1 ethylene (II)
• X and X are chloride
• p is zero.
• R and R 2 are mesityl (2,4,6-trimethylphenyl).
• n is zero.
• Exemplary catalysts of the invention are 2a and 2b, the molecular structures of which are provided above and in FIG. 2, wherein M is ruthenium, L 2 is substituted or unsubstituted pyridyl, R 1 and R 2 are mesityl (2,4,6-trimethylphenyl), Q is ethylene (II), X 1 and X 2 are chloride, Y is ethylene (II), m is 1, and n and p are zero.
• These new catalysts can be prepared by reacting RuCl 2 (sIMes)(PCy 3 )(CHPh) (Catalyst 1) and 2-(3-butenyl)pyridine in dichloromethane at 40 °C (see Example 1).
• catalyst 2a can be obtained either in pure fomi or as a mixture of isomers 2a and 2b.
• This finding was quite surprising, because the known ruthenium carbene olefin metathesis catalysts typically have a configuration like that of 2a, namely a symmetric square pyramidal geomehy where the apical position is occupied by the carbene ligand, and the equatorial positions by two trans anionic ligands and two trans neutral electron donating ligands.
• the complex is of d symmetry and contains two equatorial cis anionic ligands and two equatorial cis neutral electron donating ligands.
• this method is amenable to the synthesis of complexes (sIMes)(Cl) 2 Ru(CH(CH 2 ) 2 -C,N-2-(4-Me)-C 5 H 3 N) and Ru(CH(CH 2 ) 2 -C,N-2-(6-Me)-C 5 H 3 N), also shown in FIG. 7.
• the catalysts of the invention may be synthesized and used in catalyzing olefin metathesis reactions using the procedures described in the examples herein or variations thereof which will be apparent to one of skill in the art.
• Another embodiment of the present invention is a method for the use of the present catalysts, including 2a and 2b, for the metathesis of olefins.
• both isomers exhibit large differences in olefin metathesis activity (e.g., in RCM and ROMP). These activity differences enable tuning of the catalyst by simple isomerization of the complex in lieu of the strategies of the prior art, such as utilization of additives or complicated and time-consuming catalyst design involving ligand exchanges.
• the catalysts may be attached to a solid support; as understood in the field of catalysis, suitable solid supports may be of synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic.
• Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect, if indirect, typically between a functional group on a support surface and a ligand or substituent on the catalytic complex.
• the reactions are carried out under conditions normally used in olefin metathesis reactions catalyzed by the Grubbs family of metathesis catalysts. See, e.g., U.S. Patent Nos. 5,312,940, 5,342,909, 5,831,108, 5,969,170, 6,111,121, and 6,211,391 to Grubbs et al.
• the H NMR spectra for catalysts 2a, 4 and 5 are consistent with complexes of C s symmetry, where the resonances for each of the para methyl groups of the mesityl rings, the ortho methyl groups of the same rings and the ethylene bridge of the sIMes ligand appear as singlets [the X H SfMR singlets described are consistent with a C s symmetry and free rotation of the sIMes ligand around the Ru-C bond (on the NMR time- scale)].
• Catalyst 2b appears as a ruthenium carbene of C_ symmetry, displaying six nonequivalent methyl groups on the mesityl rings, four nonequivalent protons on the ethylene bridge of the sIMes ligand and 4 nonequivalent protons on the ethylene bridge of the pyridyl ligand in the 1H NMR spectrum.
• This geometry is typical for ruthenium olefin metathesis catalysts and is consistent with the 1H NMR spectrum of 2a.
• EXAMPLE 18 Activity of Catalysts 6 and 8: RCM of Diethylallyl Malonate [000129] As in Example 16, the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 6 and 8. In the dry box, 2.5 mol % of catalyst (0.0052 mmol) was dissolved in C 6 D 6 (0.65 mL) in an NMR tube fitted with a teflon septum screw-cap. The resulting solution was allowed to equilibrate in the NMR probe at 60 °C.
• EXAMPLE 19 ROMP of Dicvclopentadiene (DCPD) using Catalysts 2a and 2b
• DCPD Dicvclopentadiene
• the polymerization exotherms for the polymerization catalyzed by catalysts 2a and 2b were measured and are shown in FIG. 15.
• catalyst 2b is much slower that 2a in RCM, 2b also initiates the ROMP of DCPD more slowly than 2a.
• a ROMP of DCPD using 2a reaches its exotherm within 3 minutes, while the same polymerization catalyzed by 2b requires more than 25 minutes.
• the difference in reactivity between 2a and 2b may be due to the fact that the pyridine ligand in 2a is trans to the strongly ⁇ -donating NHC ligand and therefore dissociates to give the active 14-electron species much faster than in 2b.
• the difference in activity between 2a and 2b may be purely due to a disparity in initiation rates and does not give any clues regarding the conformation of the metallocyclobutane metathesis intermediates.
• EXAMPLE 21 ROMP of Dicvclopentadiene (DCPD) using Catalysts 2a, 7 and 8 [000135]
• the polymerization exotherms for the polymerization catalyzed by catalysts 2a, Ru(Ph-IM) and Ru(Cy-Im) were measured and are shown in FIG. 18.
• catalyst 7 is faster than 2a, while 8 is slower than 2a.
• Ru(R-Im) where R is for instance an alkyl or aryl group

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