WO2011056884A2 - Complexes carbéniques de sels métalliques de lithium et/ou de magnésium et leurs utilisations - Google Patents

Complexes carbéniques de sels métalliques de lithium et/ou de magnésium et leurs utilisations Download PDF

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WO2011056884A2
WO2011056884A2 PCT/US2010/055313 US2010055313W WO2011056884A2 WO 2011056884 A2 WO2011056884 A2 WO 2011056884A2 US 2010055313 W US2010055313 W US 2010055313W WO 2011056884 A2 WO2011056884 A2 WO 2011056884A2
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complex
metal
carbene
transition
group
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WO2011056884A3 (fr
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John R. Hagadorn
Matthew W. Holtcamp
Matthew S. Bedoya
Renuka N. Ganesh
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/11—Lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/22—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This invention generally relates to carbene complexes of lithium and/or magnesium metal salts and to methods of preparation thereof as well as uses of such salts in preparation of catalyst compositions.
  • transition metal complexes of cyclic alkyl amino carbenes have been found useful as catalysts for a range of applications (Bertrand et ah, U.S. 7,312,331).
  • Pd- cyclic alkyl amino carbenes complexes have been described by Bertrand and coworkers (Angew. Chem. Int. Ed. 2005, 44, 7236-7239) to be highly efficient catalysts for the alpha- arylation of ketones and aldehydes.
  • Ru-cyclic alkyl amino carbenes complexes which are have been used as catalysts for alkene metathesis processes, are also of great interest.
  • the current invention relates to a carbene complex of a lithium and/or magnesium salt useful as a synthon in the preparation of transition-metal-carbene complexes.
  • the current invention also relates to an improved synthetic route to transition-metal-carbene complexes by using a carbene complex of a lithium and/or magnesium salt as a synthon. More particularly, the present invention relates to an improved synthetic route to Ru-cyclic alkyl amino carbenes complexes using a carbene complex of a lithium and/or magnesium salt.
  • this improved synthetic route may be carried at temperatures at or above ambient, removing the need for coolants and thereby reducing the overall cost of the synthetic route.
  • the improved synthetic route using the invention described herein provides transition-metal-carbene complexes in significantly higher yields than previous reported. Accordingly, the present invention provides a facile, mild, high-yield route to transition-metal-carbene complexes.
  • This invention relates to a carbene complex of metal salt represented by the formula:
  • R is a monoanionic group
  • c is 1 or 2
  • M is a Li or Mg
  • T is a cyclic carbene ligand
  • n is selected from the group of integers comprising 1 to 24 wherein the complex has 50% or less decomposition when stored in 0.01 molar benzene at 23°C for a period of 1 hour.
  • This invention also relates to transition-metal-carbene complexes prepared from such carbene complexes of metal salts, where the transition-metal-carbene complex is preferably represented by the formula: [M*(T)(L°)q(L 1" ) s (L 2" ) t ] g , where M* is a transition metal from Group 6, 7, 8, 9, 10, 11, or 12, T is a cyclic carbene ligand, L° is a neutral ligand, L 1" is a monoanionic ligand, L 2" is a dianionic ligand, q is 0, 1, 2, 3 or 4, s is 0, 1, 2, 3, or 4, t is 0, 1, 2, 3, or 4, and g is the overall charge of the complex.
  • the transition-metal-carbene complexes may be used for synthesis reactions, including metathesis of olefins.
  • Figure 1 depicts the structure of the carbene-lithium salt adduct Compound 1 drawn with 30% thermal ellipsoids as determined by single-crystal X-ray diffraction.
  • the carbene ligand coordinated to Li(3) and the hydrogen atoms are omitted for clarity.
  • This invention generally relates to carbene complexes of lithium and/or magnesium salts, more particularly, to cyclic alkyl amino carbene (CAAC) complexes of lithium and/or magnesium salts, and even more particularly, to methods of preparation of transition-metal-carbene complexes using carbene complexes of lithium and/or magnesium metal salts in improved yields as compared to conventional routes.
  • CAAC cyclic alkyl amino carbene
  • the present invention comprises a carbene complex comprising a lithium and/or magnesium salt.
  • the present invention also relates to a novel synthetic route to transition- metal-carbene complexes, such as those useful for the cross-metathesis of olefins.
  • the present invention comprises a CAAC complex of a lithium and/or magnesium salt.
  • the present invention comprises the use of a CAAC complex of a lithium and/or magnesium salt to prepare a transition-metal-carbene complex.
  • a substituted hydrocarbyl is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom.
  • a substituted alkyl or aryl group is an alkyl or aryl radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
  • R is at least one of an alkyl sulfonate, aryl sulfonate, alkyl sulfate, aryl sulfate, carboxylate, aryl carboxylate, amidate, amidinate, thiocarboxylate, dithiocarboxylate, borate, chloride, bromide, iodide, nitrate, triflate, or perchlorate.
  • R is a triflate (OTf or TfO). Preferred triflates are represented by the Formula (A) below.
  • Preferred alkyl sulfonates are represented by the Formula (B) below, where R 2 is a Ci to C30 hydrocarbyl group, fluoro-substituted carbyl group, chloro-substituted carbyl group, aryl group, or substituted aryl group, preferably a Ci to C 12 alkyl or aryl group, preferably trifluoromethyl, methyl, phenyl, para-methyl-phenyl.
  • cyclic carbene is defined as a cyclic compound with a neutral dicoordinate carbene center featuring a lone pair of electrons.
  • Preferred cyclic carbenes are represented by the Formula (I) below: (Formula I)
  • each R* is, independently, H or a Ci to C 20 alkyl
  • each E is, independently, selected from the group comprising C, N, S, O, and P, with available valences, if any, optionally occupied by L w , L x , L y , and L z .
  • L w , L x , L y , and L z are, independently, hydrogen, hydrocarbyl groups or substituted hydrocarbyl groups.
  • L w , L x , L y , and L z are independently selected from the group consisting of hydrocarbyl groups and substituted hydrocarbyl groups having 1 to 40 carbon atoms.
  • L w , L x , L y , and L z are independently C 1-10 alkyl, substituted C 1-10 alkyl, C 2-10 alkenyl, substituted C2-10 alkenyl, C 2-10 alkynyl, substituted C 2-10 alkynyl, aryl and substituted aryl.
  • L w , L x , L y , and L z are independently selected from the group comprising methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, 2,6-diethylphenyl, 2,6- diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5-ditertbutylphenyl, 2- tertbutylphenyl, and 2,3,4,5,6-pentamethylphenyl
  • Useful substituents include C 1-10 alkyl, C2-10 alkenyl, C 2-10 alkynyl, aryl, C 1-10 alkoxy, C 2-10 alkenyloxy C 2-10 , alkynyloxy, aryloxy, C2-10 alkoxycarbonyl, C 1-10 alkylthio, C 1-10 alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • Q is carbon
  • each R* is hydrogen
  • e is 1 or 2 and d is 2.
  • L z , L x , and L y are as described above.
  • at least two of L x , L y , and L z may be joined to form a 3- to 12-membered spirocyclic ring, with available valences optionally occupied by H, oxo, halogens, hydrocarbyl, or substituted hydrocarbyl groups.
  • Useful substituents include C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, aryl, C 1-10 alkoxy, C 2-10 alkenyloxy C 2-10 , alkynyloxy, aryloxy, C 2-10 alkoxycarbonyl, C 1-10 alkylthio, C 1-10 alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • Preferred cyclic carbenes include N-heterocyclic carbenes (NHCs).
  • NHCs are cyclic carbenes of the types described above (such as by Formula I) where each E is N and the available valences on the N are occupied by L x and L y .
  • Useful NHCs are represented by the formula:
  • L x and L y are independently selected from the group comprising a hydrocarbyl group and substituted hydrocarbyl group having 1 to 40 carbon atoms.
  • L x and L y are independently selected from the group comprising C 1-10 alkyl, substituted C 1-10 alkyl, C 2-10 alkenyl, substituted C 2-10 alkenyl, C 2-10 alkynyl, substituted C 2-10 alkynyl, aryl, and substituted aryl.
  • L x and L y are independently selected from the group comprising methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5-ditertbutylphenyl, 2- tertbutylphenyl, and 2,3,4,5,6-pentamethylphenyl.
  • Useful substituents include C 1-10 alkyl, C2-10 alkenyl, C 2-10 alkynyl, aryl, C 1-10 alkoxy, C 2-10 alkenyloxy C 2-10 , alkynyloxy, aryloxy, C2-10 alkoxycarbonyl, C 1-10 alkylthio, C 1-10 alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • Some particularl useful NHCs include:
  • NHCs include the compounds described in Hermann, W. A. Chem. Eur. J. 1996, 2, 772 and 1627; Enders, D. et al, Angew. Chem. Int. Ed. 1995, 34, 1021; Alder R. W., Angew. Chem. Int. Ed. 1996, 35, 1121; and Bertrand, G. et al, Chem. Rev. 2000, 100, [0023] Particularly preferred cyclic carbenes include cyclic alkyl amino carbenes (CAACs).
  • CAACs cyclic alkyl amino carbenes
  • CAACs are cyclic carbenes as described in Formula I where one E is N and the other is C, and the available valences on the N occupied by L x , and available valences on the C are occupied by L y and L z .
  • Preferred CAACs are represented by the formula: Formula III
  • L x , L z , and L y are independently selected from the group comprising a hydrocarbyl group and substituted hydrocarbyl group having 1 to 40 carbon atoms.
  • L x , L z , and L y are independently selected from the group comprising C 1-10 alkyl, substituted C 1-10 alkyl, C 2-10 alkenyl, substituted C 2-10 alkenyl, C 2-10 alkynyl, substituted C 2-10 alkynyl, aryl, and substituted aryl.
  • L x , L z , and L y are independently selected from the group comprising methyl, ethyl, propyl, butyl (including isobutyl and n- butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, 2,6- diethylphenyl, 2,6-diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5- ditertbutylphenyl, 2-tertbutylphenyl, and 2,3,4,5,6-pentamethylphenyl.
  • Useful substituents include C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, aryl, C 1-10 alkoxy, C 2-10 alkenyloxy C 2-10 , alkynyloxy, aryloxy, C 2-10 alkoxycarbonyl, C 1-10 alkylthio, C 1-10 alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • CAACs include:
  • CAACs include the compounds described in U.S. 7,312,331 and Bertrand et al, Angew. Chem. Int. Ed. 2005, 44, 7236-7239.
  • carbenes useful in embodiments of the present invention include thiazolyidenes, P-heterocyclic carbenes (PHCs), and cyclopropenylidenes.
  • the carbene complex of a lithium and or ma nesium salt is represented by the formula:
  • M is Li or Mg (preferably Li)
  • E, R, c, n, Q, R*, e, d, L w , L x , L z , and L y are as described above.
  • the inventors have surprisingly found that certain carbene complexes comprising a lithium and/or magnesium salt form an oligomeric cluster.
  • the carbene complex comprising a lithium salt forms an oligomeric cluster.
  • the complex comprising a lithium and/or magnesium salt of a carbene forms a cube-like oligomeric cluster, where M and R groups occupy the proximate vertices of the cube, as represented by:
  • the complex of the present invention forms a cube-like oligomeric cluster, where Li and OTf groups occupy the proximate vertices of the cube, as represented by:
  • T is a CAAC of the type:
  • the carbene complexes of lithium and/or magnesium salts described above are typically prepared by contacting a protonated cyclic carbene salt with a lithium or magnesium base (preferably at -40 to 40°C, preferably above 0°C) in a non-polar solvent.
  • a non-polar solvent is defined as a solvent that contains only carbon, hydrogen and optional halogen atoms (such as an alkane, arene or halogenated hydrocarbons or halogenated aromatics), while a polar solvent is defined a solvent that contains at least one Group 15 or 16 heteroatom (such as oxygen, or sulfur). Both aliphatic and aromatic non-polar solvents are suitable for use herein.
  • Preferred non- polar solvents include benzene, toluene, hexane, pentane, isopentane, and octane.
  • the isolation of the carbene complexes of lithium and/or magnesium salts is typically accomplished by crystallization or precipitation of the complex from a non-polar solvent or mixture of non-polar solvents.
  • the carbene complexes of lithium and/or magnesium salts described above are prepared by the stepwise addition of a protonated cyclic carbene salt, as either a solid, a solution, or a slurry, to a solution of a lithium or magnesium base in a non-polar solvent.
  • the carbene complexes of lithium and/or magnesium salts described above are prepared under conditions such that the temperature is between -40 to 40°C (preferably from 0 to 40°C), the pressure is ambient, and the concentration of each reactant is between 0.00001 M and 1.0 M.
  • Suitable lithium and magnesium bases include, but are not limited to, lithium amides, magnesium amides, alkyllithiums, aryl lithiums, dialkylmagnesiums, diary lmagnesiums, and magnesium(alkyl)amides.
  • the inventors have surprisingly discovered that the carbene complexes of lithium and/or magnesium salts of the present invention display unexpected and unusual stability in both coordinating and non-coordinating solvents at or above ambient temperatures.
  • the inventors have surprisingly discovered that complexes of lithium salts of CAACs with N-substitution such as 2,6-diethylphenyl, are remarkably stable in solution at ambient temperatures.
  • solution stability studies of a complex of a particular embodiment of the present invention (Compound 1, reported in Examples 2 & 3, below) only 14% decomposition was observed in benzene at ambient temperature over a period of 4 days.
  • less than 5% decomposition was observed in tetrahydrofuran at ambient temperature over a period of 72 hours.
  • the inventors believe that the ordered oligomeric clustering observed in the carbene complexes of lithium and/or magnesium salts may provide added stability to the complex as compared to the free carbene.
  • the carbene complexes of a lithium and/or magnesium salt described above are stable at 23°C or more.
  • the carbene complexes of a lithium and/or magnesium salt described above are stable at 30°C or more, preferably at 50°C or more.
  • the carbene complexes of a lithium and/or magnesium salt described above are stable at 23°C, preferably at 30°C, preferably at 50°C.
  • the carbene complexes of a lithium and/or magnesium salt described above are stable at from -40 to 80°C, preferably from 0 to 60°C, preferably from 20 to 50°C.
  • the carbene complexes of a lithium and/or magnesium salt described above have 50%> or less (preferably 40%> or less, preferably 30%> or less, preferably 20%> or less, preferably 10% or less, preferably 5% or less) decomposition when stored in 0.01 benzene (alternately tetrahydrofuran, alternately hexane) at the selected temperature for a period of 24 hours.
  • a method for the preparation of a transition-metal-carbene complex comprises combining a transition metal reactant and at least one carbene complex of a lithium and/or magnesium salt as described above, wherein the carbene is transferred from the lithium and/or magnesium salt to the transition metal reactant.
  • a "transition metal reactant” is a compound comprising at least one transition metal with one or more coordinated ligands (the coordinated ligands are typically neutral or anionic non-metal species).
  • a "transition metal” is an element from Groups 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (including the lanthanides and actinides) of the Periodic Table, as referenced by the IUPAC in Nomenclature of Inorganic Chemistry: Recommendations 1990, G. J. Leigh, Editor, Blackwell Scientific Publications, 1990.
  • Transition metal reactants useful in embodiments of the present invention comprise transition metals (M* in the formulae below) from Group 3-12 (preferably M* is Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Fe, Ru and/or Os), more particularly Groups 6-11 (preferably M* is Cr, Co, Ni, Cu, Mn, Rh, Pd, Pt, Ag, Au, Fe, Ru and/or Os), even more particularly Group 8 (preferably M* is Fe, Ru and/or Os, preferably M* is Ru).
  • M* is Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Fe, Ru and/or Os
  • Groups 6-11 preferably M* is Cr, Co, Ni, Cu, Mn, Rh, P
  • the coordinated ligands are typically neutral or anionic non-metal species, such as trialkylphosphines, pyridines, halides, alkyls, aryls, alkylidenes, ethers, and thio ethers. Preferred examples include tricyclohexylphosphine, chlorides, substituted benzylidenes, ether substituted benzylidenes.
  • the coordinated ligands feature at least one pair of lone electrons that can form a dative or covalent bond with the transition metal.
  • the transition metal reactant features at least one labile neutral ligand, such as tricyclohexyl phosphine, which is exchanged for the cyclic carbene in the reaction.
  • the transition metal reactant is represented by the formula: where M* is a transition metal as defined above; L° is a neutral ligand; L 1" is a monoanionic ligand; L 2" is a dianionic ligand; g is the overall charge of the molecule (preferably 0, 1, or 2); q is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, or 4; and t is 0, 1, 2, 3, or 4; where g+s+2(t) is equal to the valence of the transition metal, M*.
  • "valence" is equivalent to oxidation number.
  • the overall coordination number of the transition metal is preferably 4, 5, 6, or 7.
  • the valence of the metal will be 0, 1, 2, 3, or 4.
  • each ligand may be monodentate, bidentate, tridentate, tetradentate, pentadentate, or hexadentate.
  • the transition metal reactant is a ruthenium phosphine complex.
  • Preferred ruthenium phosphine complexes are typically the combination of ruthenium and a phosphine.
  • phosphines are represented by the formula PR 9 3 , wherein each R 9 is independently hydrogen, a Ci to C 12 hydrocarbyl group, a substituted Ci to C 12 hydrocarbyl group, or a halide.
  • Preferred ruthenium phosphine complexes are represented by the formula:
  • R 10 CH (R 10 CH)j(PR 9 3 ) h RuX k
  • Examples of ruthenium phosphine complexes useful in embodiments herein include bis(tricyclohexylphosphine) benzylidine ruthenium dichloride, dichloro(o- isopropoxyphenylmethylene)(tricyclohexylphosphine) ruthenium dichloride, tris(triphenylphosphine) ruthenium dichloride, ⁇ [2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl] methylene ⁇ (tricyclohexylphosphine) ruthenium dichloride, bis(i-butylphoban)(3 -phenyl- lH-inden-l-ylidene) ruthenium dichloride, and bis(tricyclohexylphosphine)(3 -phenyl- lH-inden-l-ylidene) ruthenium dichloride.
  • the transition metal reactant may be supported on an inert material.
  • the inert material tends to render the transition metal reactant heterogeneous, which often simplifies product recovery.
  • Suitable support materials include, without limitation, silicas, aluminas, silica-aluminas, aluminosilicates, including zeolites and other crystalline porous aluminosilicates; as well as titanias, zirconia, magnesium oxide, carbon, and cross-linked, reticular polymeric resins, such as functionalized cross-linked polystyrenes, e.g., chloromethyl-functionalized cross-linked polystyrenes.
  • the transition metal reactant may be deposited onto the support by any method known to those of ordinary skill in the art, including, for example, impregnation, ion-exchange, deposition-precipitation, and vapor deposition.
  • the transition metal reactant may be chemically bound to the support via one or more covalent chemical bonds, for example, the compound may be immobilized by one or more covalent bonds with one or more of the ligands bound to the transition metal.
  • the transition metal reactant and the carbene complexes of lithium and/or magnesium salts described above may be used in various synthetic processes.
  • a transition metal reactant (as described above) and a carbene complex of a lithium and/or magnesium salt of a carbene (as described above) are combined to form a transition-metal- carbene complex wherein the carbene is transferred from the salt to the transition metal reactant.
  • the carbene is transferred from the lithium or magnesium salt to the transition metal reactant in situ.
  • the transition-metal-carbene complex is typically used in other processes such as metathesis reactions, for example, the metathesis of olefins.
  • the transition metal reactant and the carbene complex of a lithium and/or magnesium salt may be combined in any manner known in the art.
  • the transition metal reactant and the lithium or magnesium salt of a carbene may be combined in a non-coordinating solvent, in a coordinating solvent, or a mixture thereof.
  • the solvent may be polar or non-polar or may be a blend of polar and non-polar solvents.
  • Hydrocarbon solvents, both aliphatic and aromatic are suitable non-polar solvents.
  • Alkanes, such as hexane, pentane, isopentane, and octane, are useful. Alternately, mixtures of polar and non- polar solvents can be used.
  • a mixture of a non-polar aliphatic or aromatic solvent with a polar solvent particularly diethyl ether can be used.
  • Useful polar solvents include diethyl ether, methyl t-butyl ether, tetrahydrofuran, di-n-butyl ether, methyl propyl ether, di-n-propyl ether, diisopropyl ether, ethyl acetate, and acetone.
  • Preferred non-polar solvents include toluene, hexane, pentane, isopentane, and octane.
  • the carbene complex comprising a lithium and/or magnesium metal salt of a carbene may be generated in situ.
  • the carbene complexes of lithium and/or magnesium salts described above are typically formed in situ by contacting a protonated cyclic carbene salt with a lithium or magnesium base (preferably at -40 to 40°C) in a non-polar solvent.
  • the solution containing the in-situ formed lithium or magnesium salt complex can then be used in applications analogous to the isolated lithium or magnesium salt complex.
  • the in-situ reaction occurs at a temperature of -40 to 40°C, preferably 0 to 40°C, preferably 20 to 30°C.
  • in-situ is meant that the product formed in a reaction is used without being isolated from the reaction solution.
  • the product formed in the reaction is used without being substantially separated from the reaction medium (such as a solvent); preferably, the product formed in the reaction is used without being separated from the majority of the reaction medium.
  • the transfer of the carbene to the transition metal reactant may occur by coordination to the transition metal. In other embodiments, the transfer of the carbene to the transition metal reactant may occur by a substitution reaction, such as ligand exchange.
  • the reaction to form a transition-metal-carbene complex by combination of a carbene complex of a lithium or magnesium salt with a transition-metal reactant occurs at a temperature of -40 to 120°C, preferably 0 to 80°C, preferably 20 to 60°C.
  • the reaction to form a transition-metal-carbene complex by combination of a carbene complex of a lithium and/or magnesium salt with a transition-metal reactant occurs at a pressure of 0.01 to 100 atmospheres (1.01 tol0132.5 kPa ), preferably 0.8 to 2 atmospheres (81.1 to 202.7 kPa ), preferably at ambient pressure.
  • the reaction to form a transition-metal-carbene complex by combination of a carbene complex of a lithium or magnesium salt with a transition-metal reactant occurs at a concentration of reactants of 0.0000001 to 10 molar, preferably 0.0001 to 1 molar, preferably 0.01 to 1 molar.
  • M* is a transition metal as defined above; T is a cyclic carbene ligand as defined above; L° is a neutral ligand; L 1" is a monoanionic ligand; L 2" is a dianionic ligand; q is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, or 4; t is 0, 1, 2, 3, or 4; and g is the overall charge of the molecule (preferably 0, 1, or 2).
  • each ligand may be monodentate, bidentate, tridentate, tetradentate, pentadentate, or hexadentate.
  • the overall coordination number of the transition metal is preferably 4, 5, 6, or 7.
  • the valence of the metal M is g+s+2(t).
  • the valence of the metal will be 0, 1, 2, 3, or 4.
  • Preferred transition-metal-carbene complexes produced herein include:
  • transition metal carbene complexes produced herein may be used as catalysts in many other reactions such as those described by Nolan and coworkers in Chemical Reviews 2009, 109, 3612-3676. These include polymerizations, cyclizations, C-C bond formations, hydrogenations, isomerizations, hydrosilylations, hydroformylations, arylations of carbonyl compounds with boron reagents, reductions, oxidations, hydrogen/deuterium exchanges, cross coupling reactions, allylic alkylations, carbonylations, C-H bond activations, cycloisomerizations, addition reactions, telomerizations, conjugate additions, cycloadditions, and allylic alkylations.
  • transition-metal-carbene complexes produced herein may be used in many other reactions, including the metathesis of olefins.
  • these transition metal carbene complexes can be combined with a seed oil, triacylglyceride, fatty acid, fatty acid ester, and/or fatty acid alkyl ester, and an alkene such as ethylene, to make linear alpha- olefins (having at least 1 more carbon atom than the starting alkene), preferably 1-decene, 1- butene, and 1-heptene.
  • linear alpha olefins can then be used to make polyalphaolefins.
  • this invention relates to:
  • a process to produce alpha-olefm comprising contacting a seed oil with the transition-metal-carbene complexes produced herein (e.g., using a carbene complex of a lithium and or magnesium salt as a synthon), preferably with one or more of 2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride (compound D), 2-(2,6- diethylphenyl)-3,3,5,5-tetramethylpyrrolidine(o-isopropoxyphenylmethylene) ruthenium dichloride, 2-(2,4,6-trimethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride (compound D), 2-(2,
  • the seed oil is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high-oleic sunflower oil, mixtures of animal and vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil, sesame oils and mixtures thereof.
  • a process to produce alpha-olefm comprising contacting a triacylglyceride with an alkene and the transition-metal-carbene complexes produced herein (such as the complexes described in paragraph 1), preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefm comprising contacting a triacylglyceride with a transition-metal-carbene complex (preferably one or more of the compounds described in paragraph 1), preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefm comprising contacting an unsaturated fatty acid ester and or unsaturated fatty acid alkyl ester with an alkene and a transition-metal-carbene complex (preferably one or more of the compounds described in paragraph 1), preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce C 4 to C 24 linear alpha-olefm comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a transition-metal-carbene complex (preferably one or more of the compounds described in paragraph 1), wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil or algae.
  • an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a transition-metal-carbene complex (preferably one or more of the compounds described in paragraph 1), wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or
  • the inventors believe that the ordered oligomeric clustering observed in the carbene complex comprising a lithium and/or magnesium salt may provide added stability to the complex as compared to the free carbene.
  • the yield ((moles of transition-metal-carbene complex divided by moles of transition metal reactant) times 100) is at least 20%, preferably at least 30%, preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%), preferably at least 80%>.
  • this invention relates to:
  • a carbene complex of metal salt represented by the formula:
  • R is a monoanionic group; c is 1 or 2; M is a Li or Mg; T is a cyclic carbene ligand; and n is selected from the group of integers comprising 1 to 24 wherein the complex has 50% or less decomposition when stored in 0.01 molar benzene at 23°C for a period of 1 hour.
  • each R* is a hydrogen, oxo, hydrocarbyl or substituted hydrocarbyl group
  • each E is, independently, C, N, S, O, or P, with available valences, if any, occupied by L w , L x , L y , and L z , where L w , L x , L y , and L z are, independently, hydrogen, hydrocarbyl groups or substituted hydrocarbyl groups.
  • L w , L x , L y , and L z are independently Ci_io alkyl, substituted Ci_io alkyl, C 2 _io alkenyl, substituted C 2 _io alkenyl, C 2 _io alkynyl, substituted C 2 _i 0 alkynyl, aryl, and substituted aryl.
  • L w , L x , L y , and L z are independently selected from the group comprising methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5- ditertbutylphenyl, 2-tertbutylphenyl, and 2,3,4,5,6
  • Useful substituents include Ci_io alkyl, C 2 _io alkenyl, C 2 _io alkynyl, aryl, Ci_io alkoxy, C 2 _io alkenyloxy C 2 _io, alkynyloxy, aryloxy, C 2 _io alkoxycarbonyl, Ci_io alkylthio, Ci_io alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • each R is at least one of an alkyl sulfonate, aryl sulfonate, alkyl sulfate, aryl sulfate, carboxylate, aryl carboxylate, amidate, amidinate, thiocarboxylate, dithiocarboxylate, borate, chloride, bromide, iodide, nitrate, triflate, and perchlorate.
  • n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24; e is 0, 1, or 2; d is 1, 2, 3, or 4; Q is C, Si, N, P, O, or S; each R* is a hydrogen, oxo, hydrocarbyl or substituted hydrocarbyl group; and each E is, independently, C, N, S, O, or P, with available valences, if any, occupied by L w , L x , L y , and L z , where L w , L x , L y , and L z are, independently, hydrogen, hydrocarbyl groups or substituted hydrocarbyl groups.
  • M* is a transition metal from Group 6, 7, 8, 9, 10, 11, or 12; T is a cyclic carbene ligand; L° is a neutral ligand; L 1" is a monoanionic ligand; L 2" is a dianionic ligand; q is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, or 4; t is 0, 1, 2, 3, or 4; g is the overall charge of the molecule.
  • each R* is a hydrogen, oxo, hydrocarbyl or substituted hydrocarbyl group
  • each E is, independently, C, N, S, O, or P, with available valences, if any, occupied by L w , L x , L y , and L z , where L w , L x , L y , and L z are, independently, hydrogen, hydrocarbyl groups or substituted hydrocarbyl groups.
  • a process to make a transition-metal-carbene complex comprising contacting:
  • M* is a transition metal selected from Group 6, 7, 8, 9, 10, 11, or 12; L is a neutral ligand; L 1" is a monoanionic ligand; L 2" is a dianionic ligand; g is the overall charge of the molecule; q is 0, 1, 2, 3, or 4; s is 0, 1, 2, 3, or 4; and t is 0, 1, 2, 3, or 4, where g+s+2(t) is equal to the valence of the transition metal, M*.
  • each R* is a hydrogen, oxo, hydrocarbyl or substituted hydrocarbyl group
  • each E is, independently, C, N, S, O, or P, with available valences, if any, occupied by L w , L x , L y , and L z , where L w , L x , L y , and L z are, independently, hydrogen, hydrocarbyl groups or substituted hydrocarbyl groups.
  • a process to produce alpha-olefm comprising contacting algae and or a seed oil with the transition-metal-carbene complex of paragraph 15 or 16 or the transition-metal-carbene complex produced by any of any of paragraphs 17 to 23.
  • a process to produce C 4 to C 24 linear alpha-olefm comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a transition-metal-carbene complex, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil or algae, and wherein the transition-metal- carbene complex is a transition-metal-carbene complex of paragraph 15 or 16 or a transition- metal-carbene complex produced by any of any of paragraphs 17 to 23.
  • an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a transition-metal-carbene complex
  • the feed material is a
  • THF is tetrahydrofuran
  • iPr or 'Pr is isopropyl
  • Me is methyl
  • Et is ethyl
  • Tf 2 0 is trifluoromethanesulfonic anhydride
  • TfO is triflate
  • Zhan-lC is ⁇ [2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl] methylene ⁇ (tricyclohexylphosphine) ruthenium dichloride.
  • Example 1 Synthesis of 2-(2,6-diethylphenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i- propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl] methylene ruthenium dichloride (D), for comparison to Examples 2 and 3.
  • Tetrahydrofuran 40 mL was added to K (SiMe 3 ) 2 (0.379 g, 1.90 mmol) to form a homogeneous solution.
  • the solution was cooled to -80°C and then a solution of C (0.775 g, 1.90 mmol) in THF (10 mL) was added dropwise over about 10 seconds.
  • the filtrate was loaded on to a Si0 2 column (1.25" x 8") that had been packed with the same solvent mixture.
  • the column was eluted with 3 :2 hexane:CH 2 Cl 2 (300 mL) and then the solvent polarity was gradually increased to pure CH 2 C1 2 .
  • the product eluted as a dark green band. Removal of the volatiles afforded a dark green oil that crystallized upon the addition of pentane (2 mL) and cooling to -10°C overnight.
  • the product was isolated as green flocculent crystals (Compound D) that were dried under reduced pressure (0.038 g, 6.4%).
  • CeD 6 solution Compound 1 (ca. 10 mg) was combined with C 6 D 6 (1 mL) to give a clear and colorless solution. 1 H NMR spectroscopy indicated that the solution contained essentially pure (>95%) compound 1. After 4 days storage in the dark under an inert atmosphere 1 H NMR spectroscopy indicated that only 14% of compound 1 had decomposed to unidentified products.
  • D 8 -THF solution Compound 1 (ca. 10 mg) was combined with D 8 -THF (1 mL) to give a clear and colorless solution.
  • 1 H NMR spectroscopy indicated that the solution contained essentially pure (>95%) compound 1.
  • 1 H NMR spectroscopy indicated that essentially none ( ⁇ 5%) of compound 1 had decomposed.

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Abstract

Cette invention concerne un complexe carbénique de sel métallique représenté par la formule : [T-M(R)c]n. Dans cette formule, R est un groupe monoanionique; c est 1 ou 2; M est Li ou Mg; T est un ligand du type carbène cyclique; et n est choisi dans le groupe des nombres entiers allant de 1 à 24. Le complexe selon l'invention subit une décomposition de 50 % ou moins quand il est stocké dans 0,01 mole de benzène à 23°C pendant une heure. Des complexes carbéniques de métaux de transition préparés à partir des complexes carbéniques de sels métalliques selon l'invention sont également décrits, lesdits complexes carbéniques de métaux de transition étant représentés par la formule : [M*(T)(L0)q(L1-)s(L2-)t]g, où M* est un métal de transition du Groupe 6, 7, 8, 9, 10, 11 ou 12, T est un ligand du type carbène cyclique, L0 est un ligand neutre, L1- est un ligand monoanionique, L2- est un ligand dianionique, q est 0, 1, 2, 3 ou 4, s est 0, 1, 2, 3, ou 4, t est 0, 1, 2, 3, ou 4, et g est la charge globale de la molécule. Les complexes carbéniques de métaux de transition selon l'invention peuvent être utilisés pour des réactions de synthèse, dont la métathèse d'oléfines.
PCT/US2010/055313 2009-11-09 2010-11-03 Complexes carbéniques de sels métalliques de lithium et/ou de magnésium et leurs utilisations Ceased WO2011056884A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013158225A1 (fr) 2012-04-18 2013-10-24 Exxonmobil Chemical Patents Inc. Compositions de polyoléfine et leurs procédés de production
WO2015033313A3 (fr) * 2013-09-06 2015-07-30 Mandal Swadhin Kumar Complexes carbène-métal n-hétérocycliques anormaux, leurs synthèse et procédés
CN105693776A (zh) * 2016-03-08 2016-06-22 沈阳化工大学 笼状钌金属有机配合物晶体及其制备方法
US20240198321A1 (en) * 2020-07-08 2024-06-20 Centre National De La Recherche Scientifique Optically pure enantiomers of ruthenium complexes and uses thereof

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US7312331B2 (en) * 2005-06-17 2007-12-25 The Regents Of The University Of California Stable cyclic (alkyl)(amino) carbenes as ligands for transition metal catalysts

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013158225A1 (fr) 2012-04-18 2013-10-24 Exxonmobil Chemical Patents Inc. Compositions de polyoléfine et leurs procédés de production
WO2015033313A3 (fr) * 2013-09-06 2015-07-30 Mandal Swadhin Kumar Complexes carbène-métal n-hétérocycliques anormaux, leurs synthèse et procédés
CN105693776A (zh) * 2016-03-08 2016-06-22 沈阳化工大学 笼状钌金属有机配合物晶体及其制备方法
CN105693776B (zh) * 2016-03-08 2018-03-13 沈阳化工大学 笼状钌金属有机配合物晶体及其制备方法
US20240198321A1 (en) * 2020-07-08 2024-06-20 Centre National De La Recherche Scientifique Optically pure enantiomers of ruthenium complexes and uses thereof
US12168224B2 (en) * 2020-07-08 2024-12-17 Centre National De La Recherche Scientifique Optically pure enantiomers of ruthenium complexes and uses thereof

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