US20050261451A1 - Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand - Google Patents

Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand Download PDF

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US20050261451A1
US20050261451A1 US11/094,102 US9410205A US2005261451A1 US 20050261451 A1 US20050261451 A1 US 20050261451A1 US 9410205 A US9410205 A US 9410205A US 2005261451 A1 US2005261451 A1 US 2005261451A1
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substituted
hydrocarbyl
heteroatom
hydrocarbylene
alkyl
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Thay Ung
Yann Schrodi
Mark Trimmer
Andrew Hejl
Daniel Sanders
Robert Grubbs
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California Institute of Technology
Materia Inc
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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
    • C08F132/08—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 having condensed rings
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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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 V C H, 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).
  • L represents an NHC ligand such as 1,3-dimesitylimidazole-2-ylidene (IMes) and 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (sIMes)
  • X represents a halogen (e.g., Cl, Br, or I)
  • R represents an alkyl, cycloalkyl, or aryl group (e.g., butyl, cyclohexyl, or phenyl)
  • R′ represents an alkyl, alkenyl, or aryl group (e.g., methyl
  • L represents an imidazolylidine ligand
  • L′ represents a pyridine (Py) or substituted pyridine ligand
  • X represents a halogen (e.g., Cl, Br, or I
  • 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.
  • a latent olefin metathesis catalyst that contains a chelating carbene ligand is the 2-pyridylethanyl ruthenium carbene complex (PR 3 )(Cl) 2 Ru(CH(CH 2 ) 2 —C,N-2-C 5 H 4 N) by reacting a (PR 3 ) 2 (Cl) 2 Ru ⁇ CHR′ complex with 2-(3-butenyl)pyridine developed by van der Schaaf (van der Schaaf et al. (2000) J. Organometallic Chemistry 606, 65-74).
  • These types of catalysts are also described in U.S. Pat. No. 6,306,987.
  • 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)
  • a method for carrying out an olefin metathesis reaction is provided using the aforementioned complexes as reaction catalysts.
  • 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 2 a and 2 b.
  • FIG. 3 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2 a.
  • FIG. 4 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2 b.
  • 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 2 a , 4 and 5 of the invention.
  • FIG. 8 schematically depicts a method for synthesizing representative catalytic complexes 2 b 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 , 2 a , 2 b 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 2 a , 4 and 5 , as described in Example 16.
  • FIG. 12 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 2 a , 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 2 a and 2 b , as described in Example 19.
  • FIG. 16 provides the exotherms for the ROMP reaction catalyzed by catalysts 2 a , 2 b and 12 , as also described in Example 19.
  • FIG. 17 provides the exotherms for the ROMP reactions catalyzed using different mixtures of 2 a and 2 b , as described in Example 20.
  • FIG. 18 provides the exotherms for the ROMP reaction catalyzed by catalysts 2 a , 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, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms.
  • 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. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
  • alkylene refers to a 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, n-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. If not otherwise indicated, the terms “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-1,4-diene, and the like.
  • aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.
  • alkaryloxy and aralkyloxy refer to substituents of the formula —OR wherein R is alkaryl or aralkyl, respectively, as 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.
  • hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
  • heteroatom-containing hydrocarbyl group refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
  • heteroalkyl refers to an alkyl substituent that is heteroatom-containing
  • heterocyclic refers to a cyclic substituent that is heteroatom-containing
  • heteroaryl and heteroaromatic respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • 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, C 1 -C 20 alkoxy, C 2 -C 20 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 20 alkylcarbonyl (—CO-alkyl) and C 6 -C 24 arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C 2 -C 20 alkylcarbonyloxy (—O—CO-alkyl) and C 6 -C 24 arylcarbonyloxy (—O—CO-aryl)), C 2 -C 20 alkoxycarbonyl (—(CO)—O-alkyl), C 6 -C 24 aryloxycarbonyl (——C
  • 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 invention provides a Group 8 transition metal complex having the structure of formula (I)
  • 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., C 1 -C 20 alkyl, C 2 -C 20 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 C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl,
  • 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 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 alkaryl, and halide.
  • any substituents present are hydrogen, C 1 -C 12 alkyl, C 1 -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 1 and R 2 are independently selected from hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 substituted aryl, C 1 -C 20 functionalized alkyl, C 2 -C 20 functionalized alkenyl, C 2 -C 20 functionalized alkynyl, or C 5 -C 24 functionalized substituted aryl where the functional group(s) (“Fn”) may independently be one or more or the following:
  • Q is typically selected from hydrocarbylene (e.g., C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), substituted hydrocarbylene (e.g., substituted C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), heteroatom-containing hydrocarbylene (e.g., C 1 -C 20 heteroalkylene, C 2 -C 20 heteroalkenylene, C 2 -C 20 heteroalkynylene, C 5 -C 24 heteroarylene, heteroatom-containing C 6 -C 24 aralkylene, or heteroatom-containing C 6 -C 24 alkarylene
  • Q is a two-atom linkage having the structure —CR 3 R 4 —CR 5 R 6 — or —CR ⁇ CR 5 —, preferably —R 3 R 4 —CR 5 R 6 —, wherein R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
  • Examples of functional groups here include carboxyl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 24 alkoxycarbonyl, C 2 -C 24 acyloxy, C 1 -C 20 alkylthio, C 5 -C 24 arylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, optionally substituted with one or more moieties selected from C 1 -C 12 alkyl, C 1 -C 12 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, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 heteroalkyl, substituted C 1 -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.
  • 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: C 1 -C 20 alkyl, C 5 -C 24 aryl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 6 -C 24 aryloxycarbonyl, C 2 -C 24 acyl, C 2 -C 24 acyloxy, C 1 -C 20 alkylsulfonato, C 5 -C 24 arylsulfonato, C 1 -C 20 alkylsulfanyl, C 5 -C 24 arylsulfanyl, C 1 -C 20 alkylsulfinyl, C 5 -C 24
  • 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 C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, and phenyl.
  • X 1 and X 2 are halide, benzoate, C 2 -C 6 acyl, C 2 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl, phenoxy, C 1 -C 6 alkoxy, C 1 -C 6 alkylsulfanyl, aryl, or C 1 -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, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
  • 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:
  • 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.
  • L 2 is selected from NR 7 R 8 , PR 7 R 8 , N ⁇ CR 7 R 8 , and R 7 C ⁇ NR 8 , where R 7 and R 8 are independently selected from substituted and/or heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, or R 7 and R 8 taken together can form a cyclic group, e.g., piperidyl (including substituted piperidyl). Any functional groups present on L 1 , L 2 , R 7 , or R 8 will generally be selected from the Fn groups set forth above.
  • Examples of preferred such catalysts are those wherein L 2 is NR 7 R 8 , having the structure of formula (II) wherein Q, R 1 , R 2 , R 7 , R 8 , X 1 , X 2 , L 1 , Y, Z, ⁇ , and p are as defined above.
  • Preferred R 7 and R 8 substituents in this embodiment are C 1 -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.
  • L 2 and Z can be linked through an unsaturated bond, i.e., the dashed line indicating a bond at a may also represent a double bond or a bond linking adjacent atoms in an aromatic ring.
  • L 2 is selected from NR 7 and PR 7 , and preferably is NR 7 where R 7 is as defined previously.
  • the complex may be contain an imine ligand (i.e., containing the moiety —Z ⁇ NR 7 ), or may contain a pyridine ring in which N and Z are adjacent atoms in a pyridyl group. Examples of preferred such catalysts in which the complex contains a pyridine ring or an imine moiety are encompassed by structural formulae (IV) and (V), respectively:
  • R 7 substituents are C 1 -C 12 alkyl or C 5 -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 (IV) and (V) include, but are not limited to, the following:
  • Y and Z are linkages independently selected from hydrocarbylene (e.g., C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), substituted hydrocarbylene (e.g., substituted C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), heteroatom-containing hydrocarbylene (e.g., C 1 -C 20 heteroalkylene, C 2 -C 20 heteroalkenylene, C 2 -C 20 heteroalkynylene, C 5 -C 24 heteroarylene, heteroatom-containing C 6 -C 24 aralkylene, or heteroatom-containing C 6 -C
  • Organic diradicals that can serve as Y and/or Z include, by way of example, the following groups: methylene (VI), ethylene (VII), vinylene (VIII), phenylene (IX), cyclohexylene (X), and naphthylenes (XI) and (XII). These organic diradicals may also serve as the linkage Q.
  • M is ruthenium
  • Q is ethylene (II)
  • X 1 and X 2 are chloride
  • p is zero.
  • R 1 and R 2 are mesityl (2,4,6-trimethylphenyl).
  • n is zero.
  • Exemplary catalysts of the invention are 2 a and 2 b , 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 2 a can be obtained either in pure form or as a mixture of isomers 2 a and 2 b .
  • This finding was quite surprising, because the known ruthenium carbene olefin metathesis catalysts typically have a configuration like that of 2 a , namely a C S symmetric square pyramidal geometry 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 C 1 symmetry and contains two equatorial cis anionic ligands and two equatorial cis neutral electron donating ligands.
  • Catalyst 2 a can also be prepared by reaction of (sIMes)(py) 2 (Cl) 2 Ru ⁇ CHPh (complex 3 ) with 1.5 equivalent of 2-(3-butenyl)-pyridine in dichloromethane at room temperature for 30 minutes (Example 2).
  • 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 2 a and 2 b , 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. Pat. Nos. 5,312,940, 5,342,909, 5,831,108, 5,969,170, 6,111,121, and 6,211,391 to Grubbs et al.
  • a 0.1 M solution of catalyst 2 a in CD 2 Cl 2 was prepared and transferred to an NMR tube, which was capped and taken out of the glove box.
  • the NMR tube was left in an oil bath at 40° C. and the reaction was monitored by 1 H NMR spectroscopy.
  • the ratio of 2 b to 2 a in the mixture was 30/70 after 24 hours; 60/40 after 48 hours; 70/30 after 72 hours; and 78/22 after 96 hours.
  • the 1 H NMR spectra for catalysts 2 a , 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 1 H NMR 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 2 b appears as a ruthenium carbene of C 1 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 1 H NMR spectrum.
  • Pure isolated 2 a dissolved in CD 2 Cl 2 (0.1 M), is slowly converted to a 22:78 mixture of 2 a : 2 b at 40° C. over the course of 96 hours and pure isolated 2 b forms a similar mixture under the same conditions.
  • This type of ligand arrangement is relatively rare for ruthenium carbene complexes, although it has been observed in a few cases [ruthenium complexes containing chelating bisphosphine ligands and cis chlorides have been described: see, e.g., Hansen et al. (1999) Angew. Chem., Int. Ed. 38, 1273-1276; Hansen et al. (1999) Chem.
  • the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of the different catalysts.
  • 1 mol % of catalyst was added to a 0.1 M solution of diethyldiallyl malonate in dichloromethane and the reaction was allowed to proceed at 25° C. and was monitored by gas-chromatography ( FIG. 10 ).
  • 2 a is much slower than 1 ( ⁇ 20% conversion after 100 min versus ⁇ 100% conversion, respectively, under the conditions used)
  • 2 b is much slower than 2 a ( ⁇ 2% conversion after 100 min under the conditions used)
  • 12 is much slower than 2 b.
  • the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 2 a , 4 and 5 .
  • 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 40° C.
  • Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M was injected into the NMR tube neat and the reaction was monitored by 1 H NMR spectroscopy ( FIG. 11 ).
  • Example 16 the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 2 a , 7 and 8 .
  • 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 40° C.
  • Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M was injected into the NMR tube neat and the reaction was monitored by 1 H NMR spectroscopy ( FIG. 12 ).
  • catalyst 7 is faster than 2 a in RCM, while 8 is slower than 2 a.
  • Example 16 the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 6 and 8 .
  • 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.
  • Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M
  • the reaction was monitored by 1 H NMR spectroscopy ( FIG. 14 ).
  • the olefinic resonances integrals of the product relative to that of the starting material were measured with the residual protio solvent peak used as an internal standard.
  • the polymerization exotherms for the polymerization catalyzed by catalysts 2 a and 2 b were measured and are shown in FIG. 15 .
  • 2 b also initiates the ROMP of DCPD more slowly than 2 a .
  • a ROMP of DCPD using 2 a reaches its exotherm within 3 minutes, while the same polymerization catalyzed by 2 b requires more than 25 minutes.
  • the difference in reactivity between 2 a and 2 b may be due to the fact that the pyridine ligand in 2 a is trans to the strongly ⁇ -donating NHC ligand and therefore dissociates to give the active 14-electron species much faster than in 2 b .
  • the difference in activity between 2 a and 2 b may be purely due to a disparity in initiation rates and does not give any clues regarding the conformation of the metallocyclobutane metathesis intermediates.
  • the polymerization exotherms for the polymerization catalyzed by mixtures of catalysts 2 a and 2 b at various ratios of the catalysts were measured and are shown in FIG. 17 .
  • the slow isomerization process and large activity difference between catalysts 2 a and 2 b allows for this catalytic system to be tuned by partially isomerizing 2 a to a 2 a : 2 b mixture with the desired initiation rate.
  • the use of varying 2 a : 2 b mixtures for the ROMP of DCPD allowed for the control of the times to exotherm as shown in FIG. 17 .
  • the polymerization exotherms for the polymerization catalyzed by catalysts 2 a , Ru(Ph-IM) and Ru(Cy-Im) were measured and are shown in FIG. 18 .
  • catalyst 7 is faster than 2 a , while 8 is slower than 2 a .
  • the same trend was observed in the ROMP of DCPD.

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