WO1991009825A1 - Homogeneous rhenium catalysts for metathesis of olefins - Google Patents

Homogeneous rhenium catalysts for metathesis of olefins Download PDF

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WO1991009825A1
WO1991009825A1 PCT/US1991/000090 US9100090W WO9109825A1 WO 1991009825 A1 WO1991009825 A1 WO 1991009825A1 US 9100090 W US9100090 W US 9100090W WO 9109825 A1 WO9109825 A1 WO 9109825A1
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olefin
butyl
chr
compound
rhenium
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Richard R. Schrock
Robert Toreki
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Massachusetts Institute Of Technology
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    • C—CHEMISTRY; METALLURGY
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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
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • 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)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
    • 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
    • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
    • 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
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • 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
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/74—Rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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

  • Metathesis of olefins is a process that is defined as the redistribution of alkylidene moieties in a mixture of olefins to yield other olefins.
  • a stmple example of olefin metathesis is shown in equation I.
  • the reaction proceeds by addition of an olefin to a catalyst having a metal-carbon double bond.
  • olefin a catalyst having a metal-carbon double bond.
  • Three of the most active metals used in classical olefin metathesis are molybdenum, tungsten and rhenium.
  • the Edwards references describe three rhenium complexes represented by the formula Re(C-t-Bu)(CH-t-Bu)(R) 2 where R is a t-butoxide, trimethylsiloxide or neopentyl moiety.
  • R is a t-butoxide, trimethylsiloxide or neopentyl moiety.
  • none of the previously reported rhenium compounds showed any conflrmable metathesis activity in the absence of a co-catalyst or activator compound, even toward strained cyclic olefins, such as norbornene.
  • Heterogeneous rhenium catalysts (Re 2 O 7 deposited on silica and/or alumina mixtures) have been shown to metathesize methyl oleate but for a limited duration before becoming inactive.
  • the rhenium compounds comprise a rhenium (VII) atom centrally linked to an alkylidene ligand, an alkylidyne ligand and two other ligands of which at least one ligand is sufficiently electron withdrawing to render the rhenium atom electrophillc enough for metathesis reactions.
  • the electron withdrawing ligands are alkoxide groups.
  • These four-coordinate compounds are well-defined, homogeneous and isolable and can be used to catalyze the metathesis of ordinary (hydrocarbon chain) and functionalized olefins in the absence of a co-catalyst or activator compound.
  • the homogenous compounds can also catalyze the polymerization of acetylenes and ring-opening oligomerization or polynerization of cyclic olefins, such as norbornene.
  • the compounds can also be used to make other metathesis catalysts that would otherwise be difficult to synthesize.
  • R 1 is selected from the group consisting of an alkyl having 1 to 20 carbon atoms , an aryl having 6 to 20 carbon atoms , an aralkyl having 7 to 30 carbon atoms , halogen substituted derivative of each and silicon-containing analogs of each ;
  • R 2 is selected from the group consisting of R 1 or is a aubstituent re- suiting from the reaction of the Re-CHR 2 moiety of the compound with an olefin that is being metathesized;
  • R 3 and R 4 are individually selected from groups consisting of R 1 , a halogen , triflate , and concatenated coabinations of R 3 and R 4 , wherein R 3 and R 4 individually may contain alkoxide oxygen atoms which are bound to the rhenium atom;
  • n is a positive integer (preferably one or two); and provided that when R 1 and R 2 are t-butyl and R 3 and R 4 are the same, then R 3 and R
  • Rhenium compounds of the above formula are four coordinate compounds having a rhenium (VII) atom which is centrally linked to four coordinating ligands. Centrally linked is intended to mean that the rhenium atom is central to and attached to each of these ligands.
  • the alkylidyne ligand is relatively inactive while the alkylidene ligand plays an integral role in the metathesis reaction and will be described in more detail below. Examples of R 1 and R 2 include but are not Gard to phenyl, t-butyl,
  • the renaining two ligands can be any substituent which is sufficiently electron withdrawing enough to render the complex active (i.e., render the rhenium atom sufficiently alectrophilic) for metathesls reactions. While it is preferable that both ligands are electron withdrawing, the compounds of this invention may contain only one electron withdrawing ligand which is sufficiently strong enough to render the complex active for metathesis.
  • a metathesis catalyst having significant metathesis activity is one that can effect the metathesis of an ordinary or functionallzed olefin at room temperature at a rate of at least one turnover per hour, in the absence of a co-catalyst or activator compound.
  • the activity of the catalyst can be regulated by the nature of the electron withdrawing ligands.
  • an increase in catalytic activity can be achieved using a ligand which is strongly electron withdrawing.
  • R 3 and R 4 are both alkoxide ligands in which the alcohol corresponding to the electron withdrawing alkoxide ligands should have a pKa of about 9 or below.
  • Suitable electron withdrawing ligands which fall within this range include phenoxide, hexafluoro-t-butoxide and diisopropylphenoxide.
  • preferred electron withdrawing ligands include alkoxides containing 2,6-dimethylphenyl, 2,4,6- trinethylphenyl, 2,6-diisopropylphenyl, pentafluoro- phenyl, 1-methyl-1-phenyl-ethyl, 2,6-dlchlorophenyl, perchlorophenyl, trlphenylnethyl, triphenylsilyl, tri-t-butylsilyl, perfluoro-2-methyl-2-pentyl, tri- fluoro-t-butyl (CF 3 (CH 3 ) 2 C), hexafluoro-t-butyl
  • R 3 and R 4 groups are pinacolate,
  • Rhenium compounds of Formula I are typically monomers. However, they can form dimers, oligoners or polymers if the R 3 and/or R 4 substituents are small enough to permit bridging of two or more metal centers. This is commonly observed when the ligands are halogen atoms or small alkoxides. These compounds can be converted to monomeric rhenium compounds by substituting the bridging ligands with alkoxide or alkyl ligands. The substituted alkoxide or alkyl ligands should be of a sufficient size to cause the bridge between two or more rhenium compounds to break. Some examples of these rhenium compounds include the following where t-Bu represents t-butyl:
  • Complexes of this invention can optionally have one or more (preferably one or two) electron donor ligands bound to the rhenium atom.
  • the donor ligands can be ethers (e.g. diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane), nitrogen-containing bases (e.g. pyridine, quinuclidlne, t-butylamine, 2,6-dimethylaniline), and phosphorus-containing bases (e.g. triphenylphosphine, dimethylphenylphosphlne).
  • ethers e.g. diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane
  • nitrogen-containing bases e.g. pyridine, quinuclidlne, t-butylamine, 2,6-dimethylaniline
  • aost donor ligands are lost spontaneously, or are displaced readily by one or more olefins that are being metathesized and, therefore, do not prevent the metathesis reaction.
  • examples of some particularly preferred bis-alkoxide rhenium compounds of Formula II include the following where t-Bu represents t-butyl:
  • the rhenium compounds of this invention can be used as catalysts for the metathesis of ordinary olefins (hydrocarbon chain) and functionallzed olefins in a hoaogeneous phase. They can be utilized as homogeneous catalysts or can be attached covalently to inorganic (e.g. silica) or organic (e.g. polystyrene) supports to yield analogous heterogeneous catalysts. They can also function as catalysts for polymerization of acetylenes and ring-opening metathesls oligomerization or polymerization of cyclic olefins, such as norbornene. Since they are readily active compounds, they can catalyze metathesls of olefins in the absence of a co-catalyst or activator compound, such as Me 3 Sil or Lewis acids.
  • a co-catalyst or activator compound such as Me 3 Sil or Lewis acids.
  • an olefin can be metathesized by contacting it with a homogeneous rhenium metathesis catalyst in a suitable solvent, under conditions sufficient to metathesize the olefin and produce one or more metathesis products.
  • the products can then be recovered using known separation techniques or can be further metathesized.
  • the metathesls reaction proceeds by addition of an olefin to the rhenium-carbon double bond (Re-CHR 2 , a rhenium-alkylidene moiety) to form a metallacyclobutane ring (as shown below) which then releases an olefin to form a new metal-alkylidene moiety derived from the olefin.
  • Metallacyclobutane complexes which are intermediates in the metathesls reaction can also be utilized as metathesis catalysts and as catalysts for the oligomerization of acetylenes.
  • the siaplest metallacyclobutane intermediate is represented by Formula III.
  • Equation 2 The position of the equilibrium in Equation 2 will depend upon the donor ability of the solvent medium, and in the more general case where alkyl or functionallzed substituents are present in the metallacyclobutane and alkylidene complexes, upon the electronic and steric properties of those substituents.
  • the rhenium compounds of this invention can be synthesized by reacting a compound of the formula Re(MAr) 2 (CH 2 R 1 )(CHR 2 ) where Ar is selected from the group consisting of 2,6-dimethylphenyl, 2,6-dichlorophenyl and diisopropylphenyl, with HCl in a suitable solvent under conditions sufficient to produce [Re(CR 1 )(CHR 2 )(H 2 NAr)Cl 2 ] 2 .
  • Ar is diisopropylphenyl
  • the product of this reaction is a aonomer.
  • R 1 and R 2 are both t-butyl
  • the starting compound can be prepared by the sequence of reactions as described in the literature (Horton, A.D.
  • This complex is further reacted with a sodium, lithium or potassium salt of an alkoxide under conditions sufficient to produce the rhenium catalyst.
  • the electron withdrawing nature of the alkoxide should be sufficient enough to render the rhenium atom active for metathesis.
  • An alternative method for synthesizing several rhenium compounds of this invention can be performed by reacting compounds of Formula II with excess HCl or HI to produce the dlhalide, [Re(CR 1 ) (CHR 2 )X 2 ] n , where X represents a halogen atom, such as chlorine or iodine.
  • the resulting compound can be used as a precusor compound for preparing other rhenium compounds of Formula II by reacting the dlhalide with a sodium, lithium or potassium salt of an alkoxide under conditions sufficient to produce the desired rhenium catalyst.
  • the starting rhenium compounds have OR 3 ligands, such as t-butoxide and trimethylslloxide.
  • the reaction can be performed in dimethoxyethane (dme) to form the product Re(CR 1 )(CHR 2 )X 2 (dme) which can subsequently be used to produce the desired rhenium compound as previously described.
  • Equations 3, 7-9 A typical synthesis is illustrated by the sequence of reactions shown in Equations 3, 7-9.
  • An alternative synthesis is represented by Equations 3-6.
  • These reactions can be performed in suitable solvents (e.g., dimethoxyethane, methylene chloride, pentane, toluene, tetrahydrofuran (THF), or dichloromethane) and at a temperature range of from about -78oC to about 25oC.
  • suitable solvents e.g., dimethoxyethane, methylene chloride, pentane, toluene, tetrahydrofuran (THF), or dichloromethane
  • THF tetrahydrofuran
  • the synthesized products are recovered by filtering the reaction mixture and removing all solvents and readily volatile products from the filtrate in vacuo.

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Abstract

The invention pertains to rhenium (VII) compounds which are catalysts for metathesis of ordinary olefins (hydrocarbons) and functionalized olefins in a homogeneous phase and to methods of synthesizing these compounds. The rhenium compounds comprise a rhenium (VII) atom centrally linked to an alkylidene ligand, an alkylidyne ligand, and two other ligands of which at least one ligand is sufficiently electron withdrawing to render the rhenium atom significantly active for metathesis.

Description

HOMOGENEOUS RHENIUM CATALTSTS FOR METATHESIS OF OLEFINS
Background of the Invention
Metathesis of olefins is a process that is defined as the redistribution of alkylidene moieties in a mixture of olefins to yield other olefins. A stmple example of olefin metathesis is shown in equation I.
2 RHC-CHR'→ R'HC-CHR' + RHC-CHR Eq. I
The reaction proceeds by addition of an olefin to a catalyst having a metal-carbon double bond. Three of the most active metals used in classical olefin metathesis are molybdenum, tungsten and rhenium.
(Ivin, K.J., Olefin Metathesis, Acadeaic Press, London, 1983; Crubbs, R.H. in Comprehensive Organometallic Chemistry, Wilkinson, G. et al. (Eds.), Vol. 8, Fergamon: New York (1982); Dragutan, V. et al., Olefin Metathesis and Ring-Opening Polymerization of Cyclo-
Olefins, 2nd Ed., Wiley-Interscience: Hew York (1985); Leconte, M. et al. In Reactions, of Coordinated Ligands, Braterman, P.R. (Ed.), Plenum: New York (1986).) Examples of molybdenun (VI) alkylidene complexes (Murdzek, J.S. and R.R. Schrock, Organometallics 6:1373 (1987); Bazan, G. et al., Polymer Commun. 30; 258 (1989)) and tungsten (VI) alkylidene complexes have been previously described (Schrock, R.R. et al., J. Am. Chem. Soc. 110:1423 (1988); Feldman, J. et al. in Advances in Metal Carbene Chemistry, Schubert, U. (Ed.), Kluwer Acadeaic Publishers , Boston: 1989 , page 323 ; Schrock , R.R. et al., Macroaolecules 20:1169 (1987); Ginsburg, E.J. et al., J. Am. Chem. Soc.
111:7621 (1989); Swager, T.M. et al., J. Am. Chem. Soc. 111:4413 (1989); Knoll, K. and R.R. Schrock, J. Am. Chem. Soc .111:7989 (1989); Schlund, R. et al., J. Am. Chem. Soc. 111:8004 (1989)). Several of these compounds have been shown to catalyze the metathesis of olefins with an activity that can be controlled through the choice of the alkoxide ligand. For axample, tungsten and molybdenum catalysts reported by Schrock, R.R. (U.S. Patent Nos. 4,681,956 and 4,727,215) have been shown to homogeneously metathesize at least 250 equivalents of methyl oleate. Though the reported molybdenum and tungsten catalysts can metathesize ordinary olefins (hydrocarbon chains) in good yield, they are limited in their usefulness as metathesls catalyst for functionalized olefins due to their reactivity with the functional groups.
Several rhenium alkylidene complexes have also been reported (Edwards, D.S. et al., Organometallies 2:1505 (1983); Edwards, D.S., "Synthesis and Reactivity of Rhenium (VII) Neopentylidene and Neopentylidyne Complexes", MIT Doctoral Thesis (1983); Horton, A.D. et al., Organometallics 6:893 (1987); Horton, A.D. and R.R. Schrock, Polyhedron 7:1841 (1988); Cai, S. et al., J. An. Chem. Commun., 1489 (1988). In particular, the Edwards references describe three rhenium complexes represented by the formula Re(C-t-Bu)(CH-t-Bu)(R)2 where R is a t-butoxide, trimethylsiloxide or neopentyl moiety. However, none of the previously reported rhenium compounds showed any conflrmable metathesis activity in the absence of a co-catalyst or activator compound, even toward strained cyclic olefins, such as norbornene.
Heterogeneous rhenium catalysts (Re2O7 deposited on silica and/or alumina mixtures) have been shown to metathesize methyl oleate but for a limited duration before becoming inactive.
It would, therefore, be desirable to provide a homogeneous rhenlum catalyst for metathesizlng olefins, particularly functionalized olefins, at a molecular level which would be highly active, longer-lived than heterogeneous rhenium catalysts and tolerant of olefin functionalities.
Summary of the Invention
This invention pertains to four-coordinate rhenium (VII) compounds and to methods for synthesizing such compounds. The rhenium compounds comprise a rhenium (VII) atom centrally linked to an alkylidene ligand, an alkylidyne ligand and two other ligands of which at least one ligand is sufficiently electron withdrawing to render the rhenium atom electrophillc enough for metathesis reactions. Preferably, the electron withdrawing ligands are alkoxide groups.
These four-coordinate compounds are well-defined, homogeneous and isolable and can be used to catalyze the metathesis of ordinary (hydrocarbon chain) and functionalized olefins in the absence of a co-catalyst or activator compound. The homogenous compounds can also catalyze the polymerization of acetylenes and ring-opening oligomerization or polynerization of cyclic olefins, such as norbornene. The compounds can also be used to make other metathesis catalysts that would otherwise be difficult to synthesize.
Detailed Description of the Invention Four-coordinate rhenium (VII) compounds of this invention can be represented by Formula I:
[Re(CR1)(CHR2)(R3)(R4)]n I
wherein R 1 is selected from the group consisting of an alkyl having 1 to 20 carbon atoms , an aryl having 6 to 20 carbon atoms , an aralkyl having 7 to 30 carbon atoms , halogen substituted derivative of each and silicon-containing analogs of each ; R 2 is selected from the group consisting of R 1 or is a aubstituent re- suiting from the reaction of the Re-CHR 2 moiety of the compound with an olefin that is being metathesized; R 3 and R4 are individually selected from groups consisting of R1 , a halogen , triflate , and concatenated coabinations of R3 and R4 , wherein R3 and R4 individually may contain alkoxide oxygen atoms which are bound to the rhenium atom; n is a positive integer (preferably one or two); and provided that when R1 and R2 are t-butyl and R3 and R4 are the same, then R3 and R4 are groupa other than t-butoxide, trinethylsiloxide, neo- pentyl or a halogen.
Rhenium compounds of the above formula are four coordinate compounds having a rhenium (VII) atom which is centrally linked to four coordinating ligands. Centrally linked is intended to mean that the rhenium atom is central to and attached to each of these ligands. The four-coordinate compounds are characterized as having both alkylidyne (Re=CR1) and alkylidene (Re-CHR2) ligands. The alkylidyne ligand is relatively inactive while the alkylidene ligand plays an integral role in the metathesis reaction and will be described in more detail below. Examples of R1 and R2 include but are not Halted to phenyl, t-butyl,
1-methyl-1-phenyl-ethyl, trimethylsilyl, triphenyl- methyl, triphenylsilyl, tri-t-butyl, tri-t-butylsilyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl and.
2,6-dimethylphenyl. The renaining two ligands (R3 and R4) can be any substituent which is sufficiently electron withdrawing enough to render the complex active (i.e., render the rhenium atom sufficiently alectrophilic) for metathesls reactions. While it is preferable that both ligands are electron withdrawing, the compounds of this invention may contain only one electron withdrawing ligand which is sufficiently strong enough to render the complex active for metathesis. A metathesis catalyst having significant metathesis activity is one that can effect the metathesis of an ordinary or functionallzed olefin at room temperature at a rate of at least one turnover per hour, in the absence of a co-catalyst or activator compound.
The activity of the catalyst can be regulated by the nature of the electron withdrawing ligands. For instance, an increase in catalytic activity can be achieved using a ligand which is strongly electron withdrawing. Preferably, R3 and R4 are both alkoxide ligands in which the alcohol corresponding to the electron withdrawing alkoxide ligands should have a pKa of about 9 or below. Suitable electron withdrawing ligands which fall within this range Include phenoxide, hexafluoro-t-butoxide and diisopropylphenoxide. Other examples of preferred electron withdrawing ligands include alkoxides containing 2,6-dimethylphenyl, 2,4,6- trinethylphenyl, 2,6-diisopropylphenyl, pentafluoro- phenyl, 1-methyl-1-phenyl-ethyl, 2,6-dlchlorophenyl, perchlorophenyl, trlphenylnethyl, triphenylsilyl, tri-t-butylsilyl, perfluoro-2-methyl-2-pentyl, tri- fluoro-t-butyl (CF3(CH3)2C), hexafluoro-t-butyl
((CF3)2CH3C) and perfluoro-t-butyl. Examples of concatenated R3 and R4 groups are pinacolate,
2,6-dimethyl-2,6-heptanedlolate and propan-1,3-diolate. Rhenium compounds of Formula I are typically monomers. However, they can form dimers, oligoners or polymers if the R3 and/or R4 substituents are small enough to permit bridging of two or more metal centers. This is commonly observed when the ligands are halogen atoms or small alkoxides. These compounds can be converted to monomeric rhenium compounds by substituting the bridging ligands with alkoxide or alkyl ligands. The substituted alkoxide or alkyl ligands should be of a sufficient size to cause the bridge between two or more rhenium compounds to break. Some examples of these rhenium compounds include the following where t-Bu represents t-butyl:
[Re(C-t-Bu)(CH-t-Bu)Cl2]2
[Re(C-t-Bu)(CH-t-Bu)(2,6-dimethylaniline)Cl2]2
[Re(C-t-Bu)(CH-t-Bu)I2]2.
Complexes of this invention can optionally have one or more (preferably one or two) electron donor ligands bound to the rhenium atom. The donor ligands can be ethers (e.g. diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane), nitrogen-containing bases (e.g. pyridine, quinuclidlne, t-butylamine, 2,6-dimethylaniline), and phosphorus-containing bases (e.g. triphenylphosphine, dimethylphenylphosphlne).
The resulting complex is often isolable in the crystalline state. In solution, however, aost donor ligands are lost spontaneously, or are displaced readily by one or more olefins that are being metathesized and, therefore, do not prevent the metathesis reaction.
In a preferred embodiment, the compounds of the invention are represented by Formula II:
Re(CR1)(CHR2)(OR3)2 II where R1, R2 and R3 are defined above. Examples of some particularly preferred bis-alkoxide rhenium compounds of Formula II include the following where t-Bu represents t-butyl:
Re(C-t-Bu)(CH-t-Bu)(2,6-diisopropylphenoxide)2 Re(C-t-Bu)(CH-t-Bu)(ortho-t-butylphenoxide)2 Re(C-t-Bu)(CH-t-Bu)(trifluoro-t-butoxide)2 Re(C-t-Bu)(CH-t-Bu)(hexafluoro-t-butoxide)2 Re(C-t-Bu)(CH-t-Bu)(2,6-dimethylphenoxide)2.
The rhenium compounds of this invention can be used as catalysts for the metathesis of ordinary olefins (hydrocarbon chain) and functionallzed olefins in a hoaogeneous phase. They can be utilized as homogeneous catalysts or can be attached covalently to inorganic (e.g. silica) or organic (e.g. polystyrene) supports to yield analogous heterogeneous catalysts. They can also function as catalysts for polymerization of acetylenes and ring-opening metathesls oligomerization or polymerization of cyclic olefins, such as norbornene. Since they are readily active compounds, they can catalyze metathesls of olefins in the absence of a co-catalyst or activator compound, such as Me3Sil or Lewis acids.
According to the invention, an olefin can be metathesized by contacting it with a homogeneous rhenium metathesis catalyst in a suitable solvent, under conditions sufficient to metathesize the olefin and produce one or more metathesis products. The products can then be recovered using known separation techniques or can be further metathesized. The metathesls reaction proceeds by addition of an olefin to the rhenium-carbon double bond (Re-CHR2, a rhenium-alkylidene moiety) to form a metallacyclobutane ring (as shown below) which then releases an olefin to form a new metal-alkylidene moiety derived from the olefin. Since the Re-CHR2 moiety of the complex is intimately involved in the catalytic reaction, the CHR2 ligand is replaced by any other alkylidene fragment from the olefins that are being metathesized. As a result of this exchange in the alkylidene group, one can use the methods of this invention to produce rhenium catalysts having alkylidene groups which are otherwise difficult to synthesize.
Metallacyclobutane complexes which are intermediates in the metathesls reaction can also be utilized as metathesis catalysts and as catalysts for the oligomerization of acetylenes. The siaplest metallacyclobutane intermediate is represented by Formula III.
Figure imgf000011_0001
(R3O)2(R1C)ReCH2CH2CH2 III
During a metathesis reaction, the intermediates are in equilibrium with the alkylidene complex and the free olefin as depicted in Equation 2.
Figure imgf000011_0002
(R3O)2(R1C)ReCH2CH2CH2 (R3O)2(R1C)Re-CH2 +
Figure imgf000011_0003
H2C-CH2 Eq. 2
The position of the equilibrium in Equation 2 will depend upon the donor ability of the solvent medium, and in the more general case where alkyl or functionallzed substituents are present in the metallacyclobutane and alkylidene complexes, upon the electronic and steric properties of those substituents. The rhenium compounds of this invention can be synthesized by reacting a compound of the formula Re(MAr)2(CH2R1)(CHR2) where Ar is selected from the group consisting of 2,6-dimethylphenyl, 2,6-dichlorophenyl and diisopropylphenyl, with HCl in a suitable solvent under conditions sufficient to produce [Re(CR1)(CHR2)(H2NAr)Cl2]2. However, when Ar is diisopropylphenyl, the product of this reaction is a aonomer. When R1 and R2 are both t-butyl, the starting compound can be prepared by the sequence of reactions as described in the literature (Horton, A.D. and R.R. Schrock. Polyhedron 7:1841 (1988)). Other starting materials can be synthesized according to the methods described in Examples 1-3. The resulting compound is then reacted with a rigid chelating diamine in a suitable solvent under conditions sufficient to produce Re(CR1)(CHR2)(Y)Cl2, where Y represents the diamine. Preferably, the diamine is phenylenediamine or 1,8-diaminonaphthalene. However, any rigid chelating diamine will react with the rhenium complex to produce the desired product. The product is then reacted with HCl gas under conditions sufficient to yield [Re(CR1)(CHR2)Cl2]n. This complex is further reacted with a sodium, lithium or potassium salt of an alkoxide under conditions sufficient to produce the rhenium catalyst. The electron withdrawing nature of the alkoxide should be sufficient enough to render the rhenium atom active for metathesis. An alternative method for synthesizing several rhenium compounds of this invention can be performed by reacting compounds of Formula II with excess HCl or HI to produce the dlhalide, [Re(CR1) (CHR2)X2]n, where X represents a halogen atom, such as chlorine or iodine. The resulting compound can be used as a precusor compound for preparing other rhenium compounds of Formula II by reacting the dlhalide with a sodium, lithium or potassium salt of an alkoxide under conditions sufficient to produce the desired rhenium catalyst. Preferably, the starting rhenium compounds have OR3 ligands, such as t-butoxide and trimethylslloxide. When neophyl analogs are used, the reaction can be performed in dimethoxyethane (dme) to form the product Re(CR1)(CHR2)X2(dme) which can subsequently be used to produce the desired rhenium compound as previously described.
A typical synthesis is illustrated by the sequence of reactions shown in Equations 3, 7-9. An alternative synthesis is represented by Equations 3-6. These reactions can be performed in suitable solvents (e.g., dimethoxyethane, methylene chloride, pentane, toluene, tetrahydrofuran (THF), or dichloromethane) and at a temperature range of from about -78ºC to about 25ºC. The synthesized products are recovered by filtering the reaction mixture and removing all solvents and readily volatile products from the filtrate in vacuo.
In the following equations below, t-Bu-t-butyl,
Me-methyl, Ar-2,6-dimethylphenyl, OTf-OSO2CF3, pda- 1,2-phenylenediamine and R3 is previously defined. 2 (ArN)2Re(CH-t-Bu)(CH2-t-Bu) + 6HCl(g) → Eq. 3
2 ArNH3Cl + [Re(C-t-Bu) (CH-t-Bu) (H2NAr)Cl2]2
0.5[Re(C-t-Bu) (CH-t-Bu) (H2NAr)Cl2]2+2 H2N-t-Bu → Eq. 4 ArNH2 + Re(C-t-Bu) (CH-t-Bu) (H2N-t-Bu)2Cl2
Re(C-t-Bu)(CH-t-Bu)(H2N-t-Bu)2Cl2 + 2 LiOR3 → Eq. 5 2 LiCl + H2N-t-Bu + Re(C-t-Bu)(CH-t-Bu)- (OR3)2(H2N-t-Bu)
Re(C-t-Bu)(CH-t-Bu)(OR3)2(H2N-t-Bu) + MeOTf → Eq. 6 t-Bu-NH2MeOTf + Re(C-t-Bu) (CH-t-Bu) (OR3)2
0.5[Re(C-t-Bu)(CH-t-Bu)(H2NAr)Cl2]2 + pda → Eq. 7 ArNH2 + Re(C-t-Bu)(CH-t-Bu)(pda)Cl2
Re(C-t-Bu)(CH-t-Bu)(pda)Cl2 + 2HCl(g) → Eq. 8 pda 2HCl + [Re(C-t-Bu) (CH-t-Bu)Cl2]n
[Re(C-t-Bu)(CH-t-Bu)Cl2] + 2LiOR3 → Eq. 9 Re(C-t-Bu)(CH-t-Bu)(OR3)2 + 2LiCl
This invention is further illustrated by the following non-limiting examples.
In order to avoid the presence of oxygen and moisture, the latter being especially destructive, the following examples were carried out in an ataosphere of dry aolecular nitrogen using dry, pure solvents. Several of the pure, isolated products, however, are stable to oxygen and water for extended periods (several weeks). In the examples below, t-Bu-t-butyl, Me-methyl, Ar=2,6-dimethylphenyl, OAr'-2,6-diisopropylphenoxide, pda=1,2-phenylenediamine, py-pyridine and OTf=OSO2CF3.
Example 1 Preparation of Re(HAr)2Cl3py
To a stirring suspension of Re2O7 (1.0 g, 2.07 mmol) in 50 al methylene chloride was added sequentially 2,6-dimethylaniline (1.84 al, 12.4 mmol) and pyridine (3.05 ml, 78 mmol) resulting in a dark red solution. Chlorotrimethylsilane (4.8 al, 38 mmol) was then added, the solution darkened and all solids dissolved after 20 minutes. The reaction was stirred at room temperature two hours and then the dark green solution was reduced to dryness. The solids were extracted with boiling benzene and filtered through Celite™ (hydrated diatomaceous amorphous silica). Concentration of the filtrate and addition of pentane afforded Re(HAr)2Cl3py as a dark green crystalline solid (2.2 g, 86%) whose 1H NMR was identical to a compound previously reported by Horton, A.D. and R.R. Schrock, Polyhedron 7:1841 (1988).
A similar method can be used to produce Re(2,6- dilsopropylaniline)2Cl3py where 2,6-diisopropylimido is added in place of 2,6-dimethylaniline.
Example 2
Preparation of Re(N-t-Bu)2Cl3
To a stirring suspension of Re2O7 (4.0 δ, 8.26 mmol) in methylene chloride at 0ºC was added chlorotrimethylsilane (14.8 ml, 115 mmol) and then t-butylamlne (17.4 ml, 165 mmol) was added quickly dropwise. The solution instantly turned bright yellow and a white precipitate containing He3CNH3Cl formed. After stirring the solution of crude Re(N-t-Bu)3- (OSiMe3) for 20 minutes at room temperature, excess HCl(g) was bubbled through the solution. The resulting dark orange solution was then filtered and the filtrate reduced to dryness and extracted with ether. The ether extracts were then concentrated and cooled to afford large orange crystals of Re(N-t-Bu)2Cl3 (5.7 g, 79%) whose 1H MMR was identical with that previously reported by Edwards, D.S. et al., Organometallics 2:1505-1513 (1983).
Example 3 Preparation of [Re(C-t-Bu)(CH-t-Bu)(H2NAr)Cl2]2
A solution of Re(NAr)2(CH-t-Bu)(CH2-t-Bu)(4.64 g, 8.2 mmol) (Horton, A.D. and R.R. Schrock, Polyhedron 7:1841 (1988)) in dimethoxyethane was cooled to 0ºC and treated with HCl(g) (590 al, 26 mmol). The orange solution iamediately darkened and a white precipitate was observed. After stirring at 25ºC for 2.5 hours, the solvent was reaoved in vacuo leaving a beige powder that was extracted away from insoluble ArNH3Cl with benzene and filtered through a pad of Celite™. The filtrate was then reduced to dryness in vacuo and washed with pentane to yield a faintly orange powder (3.4g, 80% yield).
Anal. Calcd for Re2C36H60Cl4N2: C, 41.77; H, 5.84; H, 2.71. Found: C, 42.11; H, 6.00; N, 2.50. Partial 1H NMR (C6D6) (The compound exists as two isomers) δ 14.49, 14.48 (s, 4, CHCMe3), 2.37, 2.32, 2.28, 2.17 (s, 6 each, 2,6-Me2-C6H3), 1.39, 1.38, 1.08, 1.01 (s, 18 each. CMe3). Partial 13C(THF-d8, major isomer) δ 292.1 (CCMe3) , 286.3 (CHCMe3, JCH=130 Hz), 31.5, 28.5 (CMe3).
Example 4
Preparation of Re(C-t-Bu)(CH-t-Bu)(H2N-t-Bu)2Cl2
To an orange solution of (Re(C-t-Bu)(CH-t-Bu)- (H2NAr)Cl2]2 (0.5g, 0.48 mmol) in tetrahydrofuran was added t-butylamine (1.0 ml). The reaction mixture was stirred for twelve hours at room temperature. The solution was then reduced in volume to 5 ml and pentane was added, causing the product to crystallize from the reaction mixture as fine silky needles. (0.49g, 93% yield). The product may also be prepared in the same fashion by adding t-butylanine directly to the crude reaction product in Example 3.
1H NMR (CD2Cl2) δ 14.52 (s, 1, CHCMe3), 4.63, 4,23 (d, 2 each, NH2CHe3), 1.40, 1.36 (s, each 9, CMe3),
1.18 (s, 18, H2NCMe3). Partial 13C NMR (CD2Cl2, -60ºC) δ 298.6 (CHCMe3, JCH=131 Hz), 286.2 (CCMe3) , 29.5 (NH2CMe3), 28.8, 31.0 (CMe3).
Example 5 Preparation of Re(C-t-Bu)(CH-t-Bu)(OAr')2(H2N-t-Bu) To a -40ºC solution of Re(C-t-Bu)(CH-t-Bu)(H2N- t-Bu)2Cl2 (2.0g, 3.7 mmol) in CH2Cl2 was added solid lithium 2,6-diisopropylphenoxlde monoetherate (1.9g, 7.4 mmol). The orange solution gradually became bright yellow and was stirred at room temperature for 40 ainutes. The volatiles were then reaoved in vacuo and the solid residue extracted with pentane. The pentane extract was filtered through a pad of Celite™. Concentration and cooling of the filtrate yielded large yellow cubes (2.0g, yield = 73%). Partial 1H NMR (C6D6, varies with concentration) δ 11.15 (s, 1, CHCMe3), 3.41 (sept, 4 CHMe2) , 1.48, 0.56 (s, 9 each, CMe3). Partial 13C NMR (CD2Cl2, -60ºC) δ 293.1
(CCMe3), 234.4 (CHCMe3, JCH = 123 Hz), 51.6, 50.8, 43.9 (CMe3).
Example 6
Preparation of Re(C-t-Bu)(CH-t-Bu)(OAr')2 To a solution of Re(C-t-Bu)(OAr')2(H2N-t-Bu)
(25ag, 0.033 mmol) in C6D6 (c.a. 700 μl ) was added (via syringe) methyl triflate (3.8 μl, 0.033 mmol). A white precipitate formed within a few ainutes and was reaoved by filtration. The 1H NMR indicated a quantitative yield of Re(CCMe3) (CHCMe3) (OAr')2. This complex was stable in solution indefinitely, but was not stable in the solid state. This complex is typically generated in situ for further reactions. Partial 1H (C6D6) δ 10.72 (s, 1, CHCMe3), 3.56 (sept. 4, CHMe2), 1.19, 0.99 (s, 9 each, CMe3). Partial 13C(C6D6) δ 293.6 (CCMe3), 240.1 (CHCMe3, JCH = 125 Hz), 27.9, 23.6 (CMe3).
Example 7
Preparation of Re(C-t-Bu)(CH-t-Bu)(pda)Cl2
To a solution of [Re(C-t-Bu)(CH-t-Bu)(H2NAr)Cl2]2 (1.5g, 1.45 mmol) in tetrahydrofuran (THF) was added solid 1,2-phenylenediamine (0.32g, 2.9 mmol). The solution was stirred at room temperature 25 minutes and the solvent removed in vacuo. The solid residue was washed with pentane and then twice reprecipitated from THF/pentane to remove residual aniline. A pale orange product was obtained in 95% yield (1.39g). Partial 1H
NMR (C6D6) δ 13.42 (s, 1, CHCMe3), 1.62, 1.36 (s, 9 each, CMe6 ). Partial 13C (CD2Cl2) δ 295.6 (CCMe3)
292.0 (CHCMe3, JCH - 118 Hz), 31.2, 28.1 (CMe3).
Example 8 Preparation of [Re(c-t-Bu)(CH-t-Bu)Cl2]n
Addition of HCl(g) (98 ml, 4.4 mol) via syringe to a dimethoxyethane solution of Re(C-t-Bu)(CH-t-Bu)(pda)- Cl2 (1.0g, 1.98 mmol) resulted in the immediate formation of a white precipitate at room temperature. After 20 minutes, the precipitate was reaoved by filtration and the orange filtrate reduced to dryness. The resulting solid was washed with pentane to yield a pale orange powder (0.67g, 85%) that was insoluble in all but strongly coordinating solvents. 1H NMR
(THF-d8) δ 13.26 (s, 1, CHCMe3), 1.35, 1.26 (s, 9, CMe3). Partial 13C NMR (THF-d8) δ 239.9 (CCMe3), 285.8 (CHCMe3, JCH = 125 Hz), 31.4, 28.4 (CMe3). Example 9
Preparation of Re(C-t-Bu)(CH-t-Bu)(OC(CF3)2CH3)2
To a -40ºC THF solution of [Re(C-t-Bu)(CH-t-Bu)- Cl2]n (250 mg, 0.63 mmol) was added solid potassium hexafluoro-t-butoxide (277 mg, 1.26 mmol). The orange solution darkened as it was stirred at room temperature for 45 minutes. The solvent was then removed in vacuo and the residue extracted with pentane and filtered through a pad of Celite™. The resulting orange solution was reduced to dryness, quantitatively yielding Re(C-t-Bu)(CH-t-Bu)(OC(CF3)2CH3)2 as an orange oil. Partial 1H NMR (C6D6) δ 11.08 (s, 1. CHCMe3), 1.15. 1.13 (s, CMe3). Partial I3C NMR (C6D6) δ 295.8 (CCMe3), 248.8 (CHCMe3, JCH=127 Hz), 31.9, 29.9 (CMe3).
Example 10
Metathesis of cls-2-pentene
To 35 mg Re(C-t-Bu)(CH-t-Bu)(OC(CF3)2CH3)2 (0.05 mmol) in 5 ml of benzene was added 100 equivalents of cis-2-pentene (546 μl , 5 mmol). After 150 ainutes, gas chromatography (GC) analysis showed an approxiaately 1:2:1 mixture of 2-butenes, 2-pentenes and 3-hexenes. An additional 100 equivalents of cis-2-pentene (546 μl, 5 mmol) were then added and equilibrium was reestablished in less than 30 minutes. A 1H NMR study of the reaction of Re(C-t-Bu) (CH-t-Bu) (OC(CF3)2CH3)2 and 10 equivalents cis-2-pentene showed the presence of propagating ethylidene and propylidene species even after two days in solution. Example 11
Metathesis of Methyl Oleate
To 20 mg [Re(C-t-Bu)(CH-t-Bu)Cl2]n (0.05 mmol) as a suspension in 5 ml CH2Cl2 was added solid potassium hexafluoro-t-butoxide (22 mg, 0.10 mmol). After 30 minutes all the solids had dissolved to yield a yellow solution, and an internal standard of mesitylene and 50 equivalents of methyl oleate (850 μl, 2.5 mmol) were added. After 12 hours, the equilibrium (-1:2:1) between Me(CH2)7CH-CH(CH2)7Me, Me(CH2)7CH=CH(CH2)7CO2Me and MeO2C(CH2)7CH-CH(CH2)7CO2Me was established. The catalyst solution was then allowed to stand undisturbed for 24 hours and then an additional 50 equivalents methyl oleate (850 μl, 2.5 mmol) were added. Equilibrium was reestablished after 7.5 hours. The products of the metathesls were identified by comparison with authentic GC traces. The activity of this catalyst is at least 200 equivalents of methyl oleate and the catalytic solutions are stable for at least three days.
Example 12
Metathesis of Methyl Oleate Accelerated by Initial Reaction with 3-Hexene
To 15 ag [Re(C-t-Bu)(CH-t-Bu)Cl2]n (0.038 mmol) as a suspension in 2 ml CH2Cl2 was added solid potassium hexafluoro-t-butoxide (17 mg, 0.076 mmol). After 30 minutes, the solution was clear yellow and 10 equivalents of cis-3-hexene (47 μl, 0.38 mmol) were added. After stirring for 7 hours, 3 ml CH2Cl2, an internal standard of 1-phenyloctane and 50 equivalents of methyl oleate (640 μl, 1.9 mmol) were added. Equilibrium was established after 150 minutes, and then an additional 100 equivalents of methyl oleate (1280 μl, 3.8 mmol) were added. After six hours at room temperature, equilibrium (~1:2:1) was again achieved.

Claims

1. A homogeneous rhenium metathesis catalyst, comprising a rhenium (VII) atom centrally linked to an alkylidene ligand, an alkylidyne ligand, and two other ligands of which at least one ligand is sufficiently electron withdrawing to render the rhenium atom significantly active for metathesls.
2. The catalyst of Claim 1, wherein the electron withdrawing ligand is an alkoxide in which its corresponding alcohol has a pKa below about 9.
3. The catalyst of Claim 2, wherein the electron withdrawing ligand is selected from the group consisting of alkoxides containing 2,6-dimethyl- phenyl, 2,4,6-trimethylphenyl, 2,6-diisopropyl- phenyl, pentafluorophenyl, 2,6-dichlorophenyl, perchlorophenyl, triphenylmethyl, triphenylsilyl, tri-t-butylsilyl, perfluoro-2-,mthyl-2-pentyl, trifluoro-t-butyl, hexafluoro-t-butyl, perfluoro- t-butyl, plnacolate, 2,6-dimethyl-2,6-heptane- diolate and propan-1,3-dlolate.
4. A compound of the formula:
[Re(CR1)(CHR2)(R3)(R4)]n
wherein R1 is selected from the group consisting of an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an aralkyl having 7 to 30 carbon atoms, halogen substituted derivative of each and silicon-containing analogs of each;
R2 is selected from the group consisting of R1 or is a substltuent resulting from the reaction of the Re-CHR2 moiety of the compound with an olefin that is being metathesized;
R3 and R4 are individually selected from groups consisting of R1, a halogen, triflate, and concatenated combinations of R3 and R4; wherein R3 and R4 individually may contain alkoxide oxygen atoms which are bound to the rhenium atom; n is a positive integer; and provided that when R1 and R2 are t-butyl and R3 and R4 are the same, then R3 and R4 are groups other than t-butoxide, trimethylsiloxide, neo- pentyl or a halogen.
5. The compound of Claim 4, wherein R1 and R2 are individually selected from the group consisting of phenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropyl- phenyl, t-butyl, trimethylsilyl, triphenylmethyl, triphenylsilyl, tri-t-butyl, tri-t-butylsllyl,
1-methyl-1-phenyl ethyl and 2,6-dimethylphenyl.
6. The compound of Claim 5, wherein R3 and R4 are individually selected from the group consisting of alkoxides containing 2,6-dlmethylphenyl, 2,4,6- trimethylphenyl, 2,6-diisopropylphenyl, pentafluorophenyl, 2,6-dichlorophenyl, perchlorophenyl, triphenylmethyl, triphenylsilyl, tri- t-butylsllyl, perfluoro-2-methyl-2-pentyl, trifluoro-t-butyl, hexafluoro-t-butyl, perfluoro-t-butyl, pinacolate, 2,6-dimethyl-2,6-heptanediolate and propan-1,3- diolate.
7. The catalyst of Claim 4, further comprising an electron donor ligand bound to Re, selected from the group consisting of an ether, a nitrogen- containing base and a phosphorus-containing base.
8. The catalyst of Claim 7, wherein the donor ligand is selected from the group consisting of diethyl ether, tetrahydrofuran, 1,2-dinethoxyethane, 1,4-dioxane, pyridine, quinuclidine, t-butylamine, 2,6-dimethylaniline, triphenylphosphine and dimethylphenylphosphine.
9. A compound of the formula:
Re(CR1)(CHR2)(OR3)2
wherein R1, R2 and R3 are individually selected from the group consisting of an alkyl having one to 20 carbon atoas, an aryl having six to 20 carbon atoms, an aralkyl having seven to 30 carbon atoas, halogen substituted derivative thereof and silicon-containing analogs thereof; and R2 further consists of a substituent resulting from the reaction of the Re=CHR2 moiety of the compound with an olefin that is being metathesized, provided that when R1 and R2 are t-butyl, then R3 is a group other than t-butyl or trimethylsilyl.
10. The compound of Claim 9, wherein R1 and R2 are individually selected from the group consisting of phenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, t-butyl, trimethylsilyl, triphenylmethyl, triphenylsilyl, tri-t-butyl, tri-t-butylsilyl, 1-methyl-1-phenyl ethyl and 2,6-dimethylphenyl.
11. The compound of Claim 10, wherein R3 is selected from the group consisting of 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, pentafluorophenyl, 2,6-dichlorophenyl, perchlorophenyl, triphenylmethyl, triphenylsilyl, tri-t- butylsilyl, perfluoro-2-methyl-2-pentyl, trifluoro-t-butyl, hexafluoro-t-butyl, perfluoro- t-butyl, 2,3-dimethyl-butdiyl, 2,6-dimethyl-2,6- heptanediyl and propan-1,3-diyl.
12. The compound of Claim 9, wherein R1 and R2 are t-butyl or 1-methyl-1-phenyl-ethyl and R3 is diisopropylphenyl.
13. The compound of Claim 9, wherein R1 and R2 are t-butyl or 1-methyl-1-phenyl-ethyl and R3 is dimethylphenyl.
14. The compound of Claim 9, wherein R1 and R2 are t-butyl or 1-methyl-1-phenyl-ethyl and R3 is ortho-t-butylphenyl.
15. The compound of Claim 9, wherein R1 and R2 are t-butyl or 1-methyl-1-phenyl-ethyl and R3 is trifluoro-t-butyl or hexafluoro-t-butyl.
16. A process for metathesizlng an olefin, including the ring-opening polymerization of an olefin, comprislng the steps of: a. contacting an olefin in a aolvent with a homogeneous metathesls catalyst under conditions sufficient for metathesis, the metathesis catalyst comprising a rhenium (VII) atom centrally linked to an alkylidene ligand, an alkylidyne ligand, and two other ligands of which at least one ligand is sufficiently electron withdrawing to render the rhenium atom significantly active for metathesls, whereby the olefin is metathesized; and b. recovering one or more metathesis products.
17. The process of Claim 16, wherein the olefin is an ordinary olefin or functionallzed olefin.
18. A process for metathesizlng an olefin, including the ring-opening polymerization of an olefin, comprising the steps of: a) contacting an olefin in a solvent with a homogeneous rhenium catalyst under conditions sufficient for metathesls, the catalyst having the formula:
[Re(CR1)(CHR2)(R3)(R4)]n
wherein R1 is selected from the group consisting of an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an aralkyl having 7 to 30 carbon atoms, halogen substituted derivative of each and silicon-containing analogs of each; R2 is selected from the group consisting of
R1 or is a substituent resulting from the reaction of the Re-CHR2 moiety of the compound with an olefin that is being metathesized; R3 and R4 are individually selected from groups consisting of R1, a halogen, triflate, and concatenated combinations of R3 and R4; wherein R3 and R4 individually may contain alkoxide oxygen atoms which are bound to the rhenium atom; n is a positive integer, whereby the olefin is metathesized; and b) recovering one or more metathesls products.
19. The process of Claim 18, wherein the olefin is an ordinary olefin or functionallzed olefin.
20. The process of Claim 18, wherein R1 and R2 are t-butyl or 1-methyl-1-phenyl-ethyl and R3 is selected from the group consisting of dlmethylphenoxide, diisopropylphenoxide, hexafluoro-t-butoxide, ortho-t-butylphenoxide and t-butoxlde.
21. A process for metathesizlng an olefin, including the ring-opening polymerization of an olefin, comprising the steps of: a) contacting an olefin in a solvent with a hoaogeneous rhenium catalyst under conditions sufficient for metathesls, the catalyst having the formula:
Re(CR1)(CHR2)(OR3)2
wherein R1, R2 and R3 are the same or dif ferent and are selected from the group consisting of an alkyl having one to 20 carbon atoas, an aryl having six to 20 carbon atoms, an aralkyl having seven to 30 carbon atoms, halogen substituted derivative thereof and silicon-containing analogs thereof; and R2 further consists of a substituent re- suiting from the reaction of the Re-CHR2 moiety of the compound with an olefin that is being metathesized, whereby the olefin is metathesized; and b) recovering one or aore metathesls products.
22. The process of Claim 21, wherein the olefin is an ordinary olefin or functionallzed olefin.
23. A process for oligomerizlng or polymerizing acetylenes and cyclic olefins, comprising the steps of: a) contacting the cyclic olefin or acetylene in a solvent with a hoaogeneous rhenium catalyst under conditions sufficient to produce an oligomer or polymer, the homogeneous rhenium catalyst having the formula:
[Re(CR1)(CHR2)(R3)(R4)]n
wherein R1 is selected from the group consisting of an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, an aralkyl having 7 to 30 carbon atoms, halogen substituted derivative of each and silicon-containing analogs of each; R2 is selected from the group consisting of
R1 or is a substltuent resulting from the reaction of the Re-CHR2 moiety of the coapound with an olefin that is being metathesized; R3 and R4 are individually selected from groups consisting of R1, a halogen, triflate, and concatenated combinations of R3 and R4; wherein R3 and R4 individually may contain alkoxide oxygen atoms which are bound to the rhenium atom; n is a positive integer; and b) recovering the oligomer or polymer product.
24. The process of Claim 23, wherein the cyclic olefin is norbornene.
25. A method for preparing a homogeneous rhenium catalyst of the formula:
Re(CR1)(CHR2)(OR3)2
wherein R1, R2 and R3 are individually selected from the group consisting of an alkyl having one to 20 carbon atoas, an aryl having six to 20 carbon atoas, an aralkyl having seven to 30 carbon atoms, halogen substituted derivative thereof and silicon-containing analogs thereof; and R2 further consists of a substltuent resulting from the reaction of the Re-CHR2 moiety of the compound with an olefin that is being metathesized, comprising the steps of: a) reacting a compound of the formula
Re(NAr)2(CH2R1)(CHR2) where Ar is selected. from the group consisting of 2,6-dimethyl- phenyl, 2,6-dichlorophenyl and diisopropylphenyl, with HCl in a suitable solvent under conditions sufficient to produce [Re(CR1)(CHR2)(H2NAr)Cl2]2; wherein when Ar is diisopropylphenyl, then the product is a monomer; b) reacting the product of step (a) with a rigid chelating diamine in a suitable solvent under conditions sufficient to produce
Re(CR1)(CHR2)(Y)Cl2, where Y is the diamine; c) reacting the product of step (b) with HCl gas under conditions sufficient to yield [Re(CR1) (CHR2)Cl2]n, where n is a positive integer; and d) reacting the product of step (c) with a sodiua, lithium or potassiua salt of an alkoxide under conditions sufficient to produce the rhenium catalyst.
26. A method for preparing a homogeneous rhenium catalyst of the formula:
Re(CR1)(CHR2)(OR3)2
wherein R1, R2 and R3 are individually selected froa the group consisting of an alkyl having one to 20 carbon atoas, an aryl having six to 20 carbon atoas, an aralkyl having seven to 30 carbon atoas, halogen substituted derivative thereof and silicon-containing analogs thereof; and R2 further consists of a substituent resulting from the reaction of the Re=CHR2 moiety of the compound with an olefin that is being metathesized, comprising the steps of: a) reacting a compound of the foraula
Re(CR1)(CHR2)(OR3) with HCl in a suitable solvent under conditions sufficient to produce [Re(CR1)(CHR2)Cl2]n, wherein n is a positive integer; and b) reacting the product of step (a) with a sodium, lithium or potassium salt of an alkoxide under conditions sufficient to produce a rhenium catalyst having different OR3 ligands than the starting compound.
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Cited By (5)

* Cited by examiner, † Cited by third party
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RU2457900C1 (en) * 2011-07-19 2012-08-10 ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) Method of producing propylene and butene-1
WO2017087710A2 (en) 2015-11-18 2017-05-26 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
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US5446102A (en) * 1994-08-10 1995-08-29 Bridgeston, Corporation Olefin metathesis catalysts for degelling polymerization reactors
DE10046143A1 (en) 2000-09-15 2002-05-29 Basf Ag Supported catalysts for olefin metathesis
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057736A1 (en) * 1981-02-05 1982-08-18 Phillips Petroleum Company Olefin disproportionation process and catalyst
FR2525224A1 (en) * 1982-04-14 1983-10-21 Rhone Poulenc Chim Base Carbene type transition metal complex coordinated with Lewis acid - used as catalyst for metathesis of simple or functionalised olefin(s)
EP0191675A1 (en) * 1985-02-12 1986-08-20 Societe Nationale Elf Aquitaine Process for olefin metathesis in the presence of a complex tungsten catalyst
EP0218138A1 (en) * 1985-09-25 1987-04-15 Massachusetts Institute Of Technology New catalysts process for their production and their use for effecting metathesis of olefins

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4727215A (en) * 1985-09-25 1988-02-23 Massachusetts Institute Of Technology Catalyst composition for effecting metathesis of olefins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057736A1 (en) * 1981-02-05 1982-08-18 Phillips Petroleum Company Olefin disproportionation process and catalyst
FR2525224A1 (en) * 1982-04-14 1983-10-21 Rhone Poulenc Chim Base Carbene type transition metal complex coordinated with Lewis acid - used as catalyst for metathesis of simple or functionalised olefin(s)
EP0191675A1 (en) * 1985-02-12 1986-08-20 Societe Nationale Elf Aquitaine Process for olefin metathesis in the presence of a complex tungsten catalyst
EP0218138A1 (en) * 1985-09-25 1987-04-15 Massachusetts Institute Of Technology New catalysts process for their production and their use for effecting metathesis of olefins

Cited By (12)

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