WO2016170328A1 - Catalyseurs de tungstène - Google Patents

Catalyseurs de tungstène Download PDF

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WO2016170328A1
WO2016170328A1 PCT/GB2016/051093 GB2016051093W WO2016170328A1 WO 2016170328 A1 WO2016170328 A1 WO 2016170328A1 GB 2016051093 W GB2016051093 W GB 2016051093W WO 2016170328 A1 WO2016170328 A1 WO 2016170328A1
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alkyl
bond
formula
mao
aryl
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Dermot O'hare
Jean-Charles BUFFET
Christopher Wright
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Oxford University Innovation Ltd
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Oxford University Innovation Ltd
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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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • C07C2/06—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 alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • 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
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • 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
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • 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

  • the present invention relates to catalysts. More specifically, the present invention relates to particular Tungsten catalysts, and the use of such catalysts in alkene oligomerisation reactions.
  • W is tungsten
  • Q is O, 0->LA or N, wherein LA is a Lewis acid and is a dative bond; bond a is either a single bond or double bond;
  • bond b is a multiple bond
  • Ri , R2 and R 3 are independently selected from halo, (1 -6C)alkyl, aryl(1 - 2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl, aryl or aryl(1 - 2C)alkyl;
  • Z is a group selected from (1 -6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 , aryl(1 -2C)alkyl or an aryl optionally substituted by one or more groups selected from (1 -6C)alkyl, (3-6C)cycloalkyl, 3- to 6- membered heterocyclyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, C(0)R c , C(0)OR c , OC(0)R c , C(0)N(R b )R c , N(Rb)C(0)R
  • X is an anionic ligand
  • a catalytic composition comprising a compound of formula I as defined herein and either: (i) a suitable solid support or a suitable activator; or (ii) both a suitable solid support and a suitable activator.
  • a compound of formula I as defined herein, or a composition as defined herein in the oligomerisation of alkenes.
  • a process of forming alkene oligomers which comprises reacting alkene monomers in the presence of either:
  • alkyl as used herein includes reference to a straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
  • alkoxy as used herein include reference to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
  • aryl as used herein includes reference to an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms.
  • Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like.
  • halogen or "halo" as used herein includes reference to F, CI, Br or I. In a particular, halogen may be F or CI, of which CI is more common. Cycloalkyl
  • cycloalkyl refers to a radical of a non-aromatic cyclic hydrocarbon group, generally having from 3 to 10 ring carbon atoms (i.e. (3-10C)cycloalkyl) and zero heteroatoms in the non-aromatic ring system.
  • cycloalkyl groups include (3-nC)cycloalkyl and (3-nC)cycloalkenyl.
  • Exemplary embodiments include: cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl, cycloheptatrienyl, cyclooctyl, cyclooctenyl, bicyclo[2.2.1 ]heptanyl, bicyclo[2.2.2]octanyl, and the like.
  • heterocyclyl means a non-aromatic saturated or partially saturated monocyclic, fused, bridged, or spiro bicyclic heterocyclic ring system(s).
  • heterocyclyl includes both monovalent species and divalent species.
  • Monocyclic heterocyclic rings contain from about 3 to 12 (suitably from 3 to 6) ring atoms, with from 1 to 5 (suitably 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur in the ring.
  • Bicyclic heterocycles contain from 7 to 17 member atoms, suitably 7 to 12 member atoms, in the ring.
  • Bicyclic heterocycles contain from about 7 to about 17 ring atoms, suitably from 7 to 12 ring atoms. Bicyclic heterocyclic(s) rings may be fused, spiro, or bridged ring systems.
  • heterocyclic groups include cyclic ethers such as oxiranyl, oxetanyl, tetrahydrofuranyl, dioxanyl, and substituted cyclic ethers.
  • Heterocycles containing nitrogen include, for example, azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrotriazinyl, tetrahydropyrazolyl, and the like.
  • Typical sulfur containing heterocycles include tetrahydrothienyl, dihydro-1 ,3-dithiol, tetrahydro-2H-thiopyran, and hexahydrothiepine.
  • Other heterocycles include dihydro-oxathiolyl, tetrahydro-oxazolyl, tetrahydro-oxadiazolyl, tetrahydrodioxazolyl, tetrahydro-oxathiazolyl, hexahydrotriazinyl, tetrahydro-oxazinyl, morpholinyl, thiomorpholinyl, tetrahydropyrimidinyl, dioxolinyl, octahydrobenzofuranyl, octahydrobenzimidazolyl, and octahydrobenzothiazolyl.
  • the oxidized sulfur heterocycles containing SO or S02 groups are also included.
  • examples include the sulfoxide and sulfone forms of tetrahydrothienyl and thiomorpholinyl such as tetrahydrothiene 1 ,1 -dioxide and thiomorpholinyl 1 ,1 -dioxide.
  • heterocyclyl groups are saturated monocyclic 3 to 7 membered heterocyclyls containing 1 , 2 or 3 heteroatoms selected from nitrogen, oxygen or sulfur, for example azetidinyl, tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, morpholinyl, tetrahydrothienyl, tetrahydrothienyl 1 ,1 -dioxide, thiomorpholinyl, thiomorpholinyl 1 ,1 -dioxide, piperidinyl, homopiperidinyl, piperazinyl or homopiperazinyl.
  • any heterocycle may be linked to another group via any suitable atom, such as via a carbon or nitrogen atom.
  • reference herein to piperidino or morpholino refers to a piperidin-1 -yl or morpholin-4-yl ring that is linked via the ring nitrogen.
  • substituted as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents.
  • optionally substituted as used herein means substituted or unsubstituted.
  • substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible.
  • amino or hydroxy groups with free hydrogen may be unstable if bound to carbon atoms with unsaturated (e.g. olefinic) bonds.
  • substituents described herein may themselves be substituted by any substituent, subject to the aforementioned restriction to appropriate substitutions as recognised by the skilled person.
  • the term “optionally substituted” refers to either groups, structures, or molecules that are substituted and those that are not substituted.
  • the term "wherein a/any CH, CH 2 , CH 3 group or heteroatom (i.e. NH) within a R 1 group is optionally substituted” suitably means that (any) one of the hydrogen radicals of the R 1 group is substituted by a relevant stipulated group.
  • weight percentage refers to the percentage of said component by weight relative to the total weight of the composition as a whole. It will be understood by those skilled in the art that the sum of weight percentages of all components of a composition will total 100 wt%. However, where not all components are listed (e.g. where compositions are said to "comprise” one or more particular components), the weight percentage balance may optionally be made up to 100 wt% by unspecified ingredients (e.g. a diluent, such as water, or other nonessential ⁇ but suitable additives).
  • a diluent such as water, or other nonessential ⁇ but suitable additives
  • Lewis acid refers to a substance that can accept a pair of non-bonding electrons.
  • a Lewis acid can be defined as an electron-pair acceptor.
  • Lewis acids can include atoms, ions and molecules which are capable of accepting a pair of electrons.
  • a non-exhaustive list of Lewis acids include: Cu 2+ , Fe 2+ , Fe 3+ , BF 3 , BCI 3 , AICI 3 , AIBr 3 , SiX 4 , FeCI 3 , FeBr 3 and SnCU.
  • the term “dative bond” refers to a covalent bond formed between two atoms where both electrons come from the same atom. It is sometimes referred to as a coordinate bond.
  • ⁇ -hydrogen refers to a hydrogen atom directly bonded to a ⁇ -carbon.
  • the ⁇ carbon refers to the second carbon attached to a functional group.
  • W is tungsten
  • Q is O, 0->LA or N, wherein LA is a Lewis acid and is a dative bond; bond a is either a single bond or double bond;
  • bond b is a multiple bond
  • Ri , R2 and R 3 are independently selected from halo, (1 -6C)alkyl, aryl(1 - 2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl, aryl or aryl(1 - 2C)alkyl;
  • Z is a group selected from (1 -6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 , aryl(1 -2C)alkyl or an aryl optionally substituted by one or more groups selected from (1 -6C)alkyl, (3-6C)cycloalkyl, 3- to 6- membered heterocycle, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, C(0)R c , C(0)OR c , OC(0)R c , C(0)N(R b )R c , N(Rb)C(0)R c
  • X is an anionic ligand
  • the compounds of the invention may be used as effective alkene oligomerisation catalysts.
  • the compounds of the present invention may display superior catalytic performance when compared to current alkene oligomerisation catalysts, due to either an improved selectivity, an improved stability or an improved turnover, or combinations therefore.
  • bond b may comprise a number of different bond types (e.g. single bond, double bond, triple bond and/or dative bond).
  • bond b is selected from a single bond with a dative component, a double bond with a dative component or a double bond, such that bond b takes one of the following forms:
  • J is a coordinate (dative) bond .
  • Particular compounds of the invention include, for example, compounds of the formula (I), wherein, unless otherwise stated, each of Ri , R 2 , R3, bond a, bond b, Q, X, Z and any associated substituent group has any of the meanings defined hereinbefore or in any of paragraphs (1 ) to (40) hereinafter:- (1 ) Ri , R 2 and R 3 are independently selected from (1 -6C)alkyl, aryl(1 -2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl, aryl or aryl(1 -2C)alkyl;
  • Ri , R 2 and R 3 are independently selected from (1 -6C)alkyl, aryl(1 -2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl;
  • Ri , R 2 and R 3 are independently selected from (1 -6C)alkyl, aryl(1 -2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl, provided that said (1 -6C)alkyl, aryl(1 - 2C)alkyl or OR a group contains no ⁇ -hydrogens.
  • Ri , R 2 and R 3 are independently selected from (1 -6C)alkyl or aryl(1 -2C)alkyl, provided that said (1 -6C)alkyl or aryl(1 -2C)alkyl group contains no ⁇ -hydrogens.
  • Ri , R 2 and R 3 are independently selected from methyl, benzyl or a group of the formula:
  • R d is selected from a (1 -2C)alkyl
  • Ri , R 2 and R 3 are independently selected from methyl or a group of the formula:
  • R d is selected from a (1 -2C)alkyl
  • Ri , R 2 and R 3 are methyl
  • bond a is a single bond
  • (10) bond b is a single bond with a dative component, a double bond or a double bond with a dative component
  • (1 1 ) bond b is a double bond or a double bond with a dative component
  • (12) bond b is a double bond
  • Q is C ⁇ LA or N, wherein LA is a BF 3 , BCI 3 , AICI 3 , AIBr 3 ,SiX 4 , FeCI 3 , FeBr 3 or SnCU and is a dative bond;
  • Q is 0->LA or N, wherein LA is a AICI 3 or BF 3 and is a dative bond;
  • X is selected from halo, OAc, hydride, phosphonate, sulphonate, borate, cyclopentadienyl, pentamethylcyclopentadienyl, or pentamethylindenyl or indenyl;
  • X is selected from halo, OAc, hydride, cyclopentadienyl, pentamethylcyclopentadienyl, indenyl or pentamethylindenyl;
  • X is selected from halo, OAc, hydride, phosphonate, sulphonate, borate, or (1 - 4C)alkoxy;
  • X is selected from halo, OAc or hydride
  • X is selected is CI, Br or I;
  • (23) Z is selected from (1 -6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , aryl(1 -2C)alkyl or an aryl, wherein said aryl is optionally substituted by one or more groups selected from (2-6C)alkyl, (3-6C)cycloalkyl, 3- to 6-membered heterocycyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,ORb, NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, C(0)R c , C(0)OR c , OC(0)R c , C(0)N(Rb)R c , N(Rb)C(0)R c , S(0) y R b (where
  • Z is selected from (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a phenyl, wherein said phenyl is optionally substituted by one or more groups selected from (2-6C)alkyl, (3-6C)cycloalkyl, 3- to 6-membered heterocycyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,ORb, NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, and wherein R b is selected from (1 -6C)alkyl, (3-6C)cycloalkyl, aryl or aryl(1 -2C)alkyl and R c is selected from H or (1 -6C)alkyl;
  • (26) Z is selected from (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a phenyl, wherein said phenyl is optionally substituted by one or more groups selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, and wherein R b and R c are independently selected from H or (1 - 6C)alkyl;
  • Z is selected from (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a phenyl, wherein said phenyl is optionally substituted by one or more groups selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 ,OR b , NR b R c , halo, amino, cyano, nitro, and wherein R b and R c are independently selected from H or (1 -4C)alkyl;
  • Z is selected from (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a phenyl, wherein said phenyl is optionally substituted by one or more groups selected from (2-4C)alkyl, SiMe 3 or OMe;
  • Z is an aryl substituted by one or more groups selected from (2-6C)alkyl, (3- 6C)cycloalkyl, 3- to 6-membered heterocycyl, Si[(1 -4C)alkyl] 3 , Si[0(1 - 4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, C(0)R c , C(0)OR c , OC(0)R c , C(0)N(R b )R c , N(R b )C(0)R c , S(0) y R b (where y is 0, 1 or 2), or (CH 2 ) z NR b R c (where z is 1 or 2), and wherein R b is selected from (1 -6C)alkyl, (3-6
  • (30) Z is a phenyl substituted by one or more groups selected from (2-6C)alkyl, (3- 6C)cycloalkyl, 3- to 6-membered heterocycyl, Si[(1 -4C)alkyl] 3 , Si[0(1 - 4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo or amino, wherein R b is selected from (1 - 6C)alkyl, (3-6C)cycloalkyl, aryl or aryl(1 -2C)alkyl and R c is selected from H or (1 - 6C)alkyl;
  • (31 ) Z is a phenyl substituted by one or more groups selected from (2-6C)alkyl, (3- 6C)cycloalkyl, 3- to 6-membered heterocycyl, Si[(1 -4C)alkyl] 3 , Si[0(1 - 4C)alkyl)] 3 ,ORb, NR b R c , aryl, halo or amino, wherein R b is selected from (1 - 6C)alkyl, (3-6C)cycloalkyl, aryl or aryl(1 -2C)alkyl and R c is selected from H or (1 - 6C)alkyl;
  • (32) Z is a phenyl substituted by one or more groups selected from (2-6C)alkyl, (3- 6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo or amino, wherein R b and R c are independently selected from H or (1 -6C)alkyl;
  • Z is (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a group of the formula:
  • R e and Rf are independently selected from hydrogen, (2-6C)alkyl, (3- 6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR h , NR h Ri, aryl, halo or amino, wherein R h and R, are independently selected from H or (1 -6C)alkyl; and
  • R g is selected from hydrogen, (1 -4C)alkyl or (1 -4C)alkoxy;
  • Z is (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a group of the formula:
  • R e and Rf are independently selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR h , NRhRi, aryl, halo or amino, wherein R h and Ri are independently selected from H or (1 -6C)alkyl; and R g is selected from hydrogen, (1 -4C)alkyl or (1 -4C)alkoxy;
  • Z is (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a group of the formula:
  • R e and Rf are independently selected from (2-6C)alkyl, ORh Or NR h Ri, wherein R h and R, are independently selected from H or (1 -6C)alkyl;
  • R g is selected from hydrogen, (1 -4C)alkyl or (1 -2C)alkoxy;
  • Z is (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a group of the formula:
  • R e and R f are independently selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR h , NRhRi, aryl, halo or amino, wherein R h and Ri are independently selected from H or (1 -6C)alkyl;
  • Z is a group of the formula:
  • R e and R f are independently selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR h , NRhRi, aryl, halo or amino, wherein R h and Ri are independently selected from H or (1 -6C)alkyl; (38) Z is a group of the formula:
  • R e and Rf are independently selected from (2-6C)alkyl, (Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,ORh or NR h Ri, wherein R h and R, are independently selected from H or (1 -6C)alkyl;
  • Z is a group of the formula:
  • R e and Rf are independently selected from (2-6C)alkyl, ORh or NR h R, wherein R h and R, are independently selected from H or (1 -6C)alkyl;
  • (40) Z is 2,6-diisopropylphenyl.
  • (41 ) Z is phenyl substituted with 1 , 2 or 3 substituents selected from methyl, methoxy, halo and trifluoromethyl.
  • Z is phenyl substituted with 1 or 3 methyl substituents, or 1 , 2 or 3 substituents selected from halo, methoxy and trifluoromethyl.
  • (45) Z is selected from:
  • the compounds of the invention are the compounds of formula (I) wherein:
  • Ri , R 2 and R 3 are as defined in any one of paragraphs (5) to (7);
  • bond b is as defined in any one of paragraphs (10) to (12);
  • X is as defined in any one of paragraphs (20) to (22).
  • R 3 is methyl, i.e. the compounds have the structural formula la (a sub-definition of formula (I)) shown below:
  • Ri and R 2 are as defined in any one of paragraphs (1 ) to (7); bond a is as defined in any one of paragraphs (8) to (9); bond b is as defined in any one of paragraphs (10) to (12) Q is as defined in any one of paragraphs (13) to (16);
  • Ri and R 2 are as defined in any one of paragraphs (1 ) to (7); bond a is as defined in paragraph (8);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri and R 2 are as defined in any one of paragraphs (5) to (7); bond a is as defined in paragraph (8);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri and R 2 are as defined in any one of paragraphs (5) to (7); bond a is as defined in paragraph (8);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • Ri and R 2 are as defined in any one of paragraphs (6) to (7); bond a is as defined in paragraph (8);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • R 2 and R 3 are methyl, i.e. the compounds have the structural formula lb (a sub-definition of formula (I)) shown below:
  • Ri is as defined in any one of paragraphs (1 ) to (7);
  • bond a is as defined in any one of paragraphs (8) to (9);
  • bond b is as defined in any one of paragraphs (10) to (12);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri is as defined in any one of paragraphs (1 ) to (7);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri is as defined in any one of paragraphs (5) to (7);
  • Ri is as defined in any one of paragraphs (5) to (7);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • Ri is as defined in any one of paragraphs (6) to (7);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • bond b is as defined in any one of paragraphs (10) to (12);
  • X is as defined in any one of paragraphs (17) to (22).
  • X is as defined in any one of paragraphs (19) to (22).
  • X is as defined in paragraph (22).
  • X is as defined in any one of paragraphs (17) to (22).
  • X is as defined in any one of paragraphs (16) to (21 ).
  • X is as defined in any one of paragraphs (16) to (21 ).
  • X is as defined in any one of paragraphs (16) to (21 ).
  • X is as defined in paragraph (21 ).
  • R e , Rf, R g , bond b and X each have any one of the meanings defined herein.
  • bond b is as defined in any one of paragraphs (10) to (1 2);
  • R e and Rf are as defined in paragraph (33);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in any one of paragraphs (17) to (22).
  • bond b is as defined in paragraph (12) ;
  • R e and Rf are as defined in paragraph (30);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • bond b is as defined in paragraph (12) ;
  • R e and Rf are as defined in paragraph (30);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in paragraph (22).
  • bond b is as defined in paragraph (12) ;
  • R e and Rf are as defined in paragraph (30);
  • R g is as defined in paragraph (35).
  • X is as defined in paragraph (22).
  • Q is N
  • Ri , R 2 and R 3 are methyl
  • bond a is a single bond
  • bond b is a double bond
  • Z is as shown below, i.e. the compounds have the structural formula le (a sub-definition of formula (I)) shown below:
  • R e , Rt and X each have any one of the meanings defined herein.
  • R e and Rf are as defined in any one of paragraphs (36) to (39);
  • X is as defined in any one of paragraphs (17) to (22).
  • R e and Rf are as defined in any one of paragraphs (36) to (39);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • R e and Rf are as defined in any one of paragraphs (38) to (39);
  • X is as defined in any one of paragraphs (21 ) to (22).
  • Z is as shown below, i.e. the compounds have the structural formula If (a sub-definition of formula (I)) shown below:
  • Ri , R 2 , R3, bond a, bond b, Q, X, R e , Rf and R g have any one of the meanings defined herein.
  • Ri , R2 and R 3 are as defined in any one of paragraphs (1 ) to (7);
  • bond a is as defined in any one of paragraphs (8) to (9);
  • bond b is as defined in any one of paragraph (10) to (12);
  • R e and Rf are as defined in paragraph (33);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri , R2 and R 3 are as defined in any one of paragraphs (1 ) to (7);
  • R e and Rf are as defined in paragraph (33);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in any one of paragraphs (17) to (22).
  • Ri , R2 and R 3 are as defined in any one of paragraphs (5) to (7);
  • R e and Rf are as defined in paragraph (33);
  • R g is as defined in any one of paragraphs (33) to (35);
  • X is as defined in any one of paragraphs (20) to (22).
  • Ri , R2 and R 3 are as defined in any one of paragraphs (6) to (7);
  • R e and Rf are as defined in paragraph (33);
  • R g is as defined in paragraph (35).
  • X is as defined in any one of paragraphs (21 ) to (22).
  • Particular compounds of the present invention include any of the compounds exemplified in the present application, and, in particular, the following compound:
  • the compound of formula (I) has a structure according to any of the following:
  • the compounds of the present invention may additionally be limited by one or both of the following provisos:
  • tungsten is in oxidation state (VI).
  • the compounds of the present invention may be converted into another catalytically active species during their use in catalytic applications.
  • a person skilled in the art will appreciate that the compounds administered in the catalytic process may themselves be the active catalytic species or may be converted into another active catalytic species during the course of the reaction.
  • the person skilled in the art would also appreciate the likely forms of the active species in such catalytic reactions.
  • a non- limiting example of such conversion would be where W(NAr)Me3CI, wherein Ar is 2,6- diisopropylphenyl, is converted into W(NAr)CH 2 Me 2 or W(NAr)CH 2 MeCI (shown below) during the course of the reaction.
  • any of the above structures may also include an additional bond from N to W of dative character.
  • the compounds of this invention may possess one or more asymmetric centres; such compounds can therefore be produced as individual (R)- or (S)-stereoisomers or as mixtures thereof.
  • the description or naming of a particular compound in the specification and claims is intended to include both individual enantiomers and mixtures, racemic or otherwise, thereof.
  • the methods for the determination of stereochemistry and the separation of stereoisomers are well-known in the art (see discussion in Chapter 4 of "Advanced Organic Chemistry", 4th edition J. March, John Wiley and Sons, New York, 2001 ), for example by synthesis from optically active starting materials or by resolution of a racemic form. It is to be understood that the present invention encompasses all optical, diastereoisomers and geometric isomers and mixtures thereof that possess catalytic activity.
  • the present invention also encompasses compounds of the invention as defined herein which comprise one or more isotopic substitutions.
  • H may be in any isotopic form, including 1 H, 2H(D), and 3H (T);
  • C may be in any isotopic form, including 12C, 13C, and 14C; and
  • O may be in any isotopic form, including 160 and 180; and the like.
  • the present invention provides a catalytic composition comprising a compound of formula I as defined herein and either: (i) a suitable solid support or a suitable activator; or (ii) both a suitable solid support and a suitable activator.
  • the compounds of the invention are immobilized on a suitable solid support as defined herein.
  • the compounds of the invention may be immobilized directly on the solid support, or via a suitable linker.
  • the compounds of the invention may be immobilized on the solid support by one or more ionic or covalent interactions. Immobilizing the compounds of the present invention on a suitable solid support may result in superior performance in the oligomerisation of alkenes. In particular, the immobilizing the compounds of the present invention on a suitable solid support may improve product separation and catalyst recovery.
  • the compound of formula I is immobilized on the solid support.
  • the compound of the invention may be immobilized directly on the solid support, or via a suitable linker.
  • the compound of the invention is immobilized on the solid support by one or more ionic or covalent interactions.
  • the solid support may also be an activator.
  • a suitable activator is something that helps mediate, initiate or enhance the catalytic reaction.
  • activator may be used synonymously with the term "co-catalyst”.
  • Suitable activators include, but are not limited to, aluminium derivatives (e.g. trimethylaluminium (TMA), dimethyl aluminiumchloride (DMAC), methylaluminiumdichloride (AIMeCI 2 ), methylaluminoxane (MAO), polymethylaluminoxane, tri(isobutyl)aluminium (TIBA) and triethylaluminium (TEA)).
  • TMA trimethylaluminium
  • DMAC dimethyl aluminiumchloride
  • AIMeCI 2 methylaluminiumdichloride
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TAA triethylaluminium
  • the suitable activator is selected from trimethylaluminium (TMA), methylaluminoxane (MAO), polymethylaluminoxane, tri(isobutyl)aluminium (TIBA) or triethylaluminium (TEA).
  • TMA trimethylaluminium
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TEA triethylaluminium
  • the suitable activator is methylaluminoxane (MAO).
  • Suitable solid supports are also well known in the art and include, but are not limited to, silica, silica-MAO, polymethylaluminoxane (also known as 'solid MAO'), a layered double hydroxide (LDH), LDH-MAO, aqueous miscible organic layered double hydroxides (AMO-LDHs), zirconia and titania.
  • the solid support is selected from silica-MAO, polymethylaluminoxane (also known as 'solid MAO'), a layered double hydroxide (LDH), LDH-MAO.
  • silica-MAO denotes MAO activated silica
  • LDH- MAO denotes MAO activated layered double hydroxide.
  • the layered double hydroxide of the suitable solid support is of the formula:
  • M ⁇ and M ,y ⁇ are two (or more) different charged metal cations
  • b is 0 to 10;
  • c is 0.0 to 10, preferably c > 0.01 and ⁇ 10,
  • X n_ is an anion with n > 0, preferably 1 -5
  • the AMO-solvent is an aqueous miscible organic solvent.
  • the layered double hydroxide of the suitable solid support is of the formula ⁇ [Mg(i-x)Alx(OH) 2 ] a+ (wherein X is selected from C0 3 , N0 3 or S0 4 ).
  • the solid support is provided as an activator.
  • the activated support is insoluble under the polymerisation conditions.
  • b is a number less than 1 , b is 0 or a number greater than 0 which gives compounds optionally hydrated with a stoichiometric amount or a non-stoichiometric amount of water and/or an aqueous- miscible organic solvent (AMO-solvent), such as acetone.
  • AMO-solvent aqueous- miscible organic solvent
  • the solid support is Solid MAO.
  • Solid methyl aluminoxane (often referred to as polymethylaluminoxane) is distinguished from other methyl aluminoxanes (MAOs) as it is insoluble in hydrocarbon solvents and so acts as a heterogeneous support system. Any suitable solid MAO support may be used.
  • solid MAO In contrast to non-solid (hydrocarbon-soluble) methyl aluminoxanes, which are traditionally used as an activator species in slurry polymerisation or to modify the surface of a separate solid support material (e.g. Si0 2 ), solid MAO is itself suitable for use as a support material, without the need for an additional activator.
  • the solid MAO is prepared by heating a solution containing polymethylaluminoxane and a hydrocarbon solvent (e.g. toluene), so as to precipitate solid MAO.
  • the solution containing polymethylaluminoxane and a hydrocarbon solvent may be prepared by reacting trimethyl aluminium and benzoic acid in a hydrocarbon solvent (e.g. toluene), and then heating the resulting mixture.
  • the solid polymethylaluminoxane is prepared according to the following protocol:
  • the properties of the solid polymethylaluminoxane can be adjusted by altering one or more of the processing variables used during its synthesis.
  • the properties of the solid polymethylaluminoxane may be adjusted by varying the Al:0 ratio, by fixing the amount of AIMe 3 and varying the amount of benzoic acid.
  • Exemplary Al:0 ratios are 1 :1 , 1 .1 :1 , 1 .2:1 , 1 .3:1 , 1 .4:1 and 1 .6:1 .
  • the Al:0 ratio is 1 .2:1 or 1 .3:1 .
  • the properties of the solid polymethylaluminoxane may be adjusted by fixing the amount of benzoic acid and varying the amount of AIMe 3 .
  • the solid polymethylaluminoxane is prepared according to the following protocol:
  • steps 1 and 2 may be kept constant, with step 2 being varied.
  • the temperature of step 2 may be 70-100°C (e.g. 70°C, 80°C, 90°C or 100°C).
  • the duration of step 2 may be from 12 to 28 hours (e.g. 12, 20 or 28 hours).
  • the duration of step 2 may be from 5 minutes to 24 hours.
  • Step 3 may be conducted in a solvent such as toluene.
  • the aluminium content of the solid polymethylaluminoxane falls within the range of 36-41 wt%.
  • the solid MAO support is insoluble in benzene, toluene and hexane.
  • the solid polymethylaluminoxane useful as part of the present invention is characterised by extremely low solubility in toluene and n-hexane.
  • the solubility in n-hexane at 25°C of the solid polymethylaluminoxane is 0-2 mol%.
  • the solubility in n-hexane at 25°C of the solid polymethylaluminoxane is 0-1 mol%.
  • the solubility in n-hexane at 25 °C of the solid polymethylaluminoxane is 0-0.2 mol%.
  • the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-2 mol%.
  • the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-1 mol%.
  • the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-0.5 mol%.
  • the solubility in solvents can be measured by the method described in JP-B(KOKOKU)-H07 42301 .
  • the solid MAO support is in particulate form.
  • the particles of the solid MAO support are spherical, or substantially spherical, in shape.
  • the solid MAO support is as described in US2013/0059990, WO2010/055652 or WO2013/146337 and obtainable from Tosoh Finechem Corporation, Japan.
  • the composition comprises solid MAO as the suitable solid support, wherein the solid support functions as an activator, and, optionally, another activator selected from methylaluminoxane (MAO), polymethylaluminoxane, tri(isobutyl)aluminium (TIBA) or triethylaluminium (TEA).
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TAA triethylaluminium
  • the compounds of the invention may be associated with the solid support by any suitable means.
  • the compounds of the invention may be bonded to the solid support via one or more ionic or covalent interactions.
  • the reaction scheme below provides a schematic illustration of how W(NDipp)Me 3 CI (derived from W(NDipp)CI 4 (THF)) may be associated with solid MAO.
  • the compounds of the present invention can be prepared by any suitable technique known in the art. Particular processes for the preparation of these compounds are described further in the accompanying examples.
  • R is selected from Ri , R 2 or R 3 which are as defined hereinbefore).
  • the compound of formula A is provided as a solvate.
  • the compound of formula A may be provided as an ether (e.g. Et 2 0) solvate.
  • Any suitable solvent may be used in the synthesis defined above.
  • a particularly suitable solvent is toluene, benzene or THF.
  • a most suitable solvent is benzene.
  • reaction conditions e.g. temperature, pressures, reaction times, agitation etc.
  • the present invention provides the use of compounds of formula (I) as defined herein, or a catalytic composition as defined herein, as an alkene oligomerisation catalyst.
  • catalytic compositions used may be any of the catalytic compositions defined herein.
  • the compounds of the invention may be used as effective alkene oligomerisation catalysts.
  • the compounds of the present invention may display superior catalytic performance when compared to current alkene oligomerisation catalysts, due to either an improved selectivity, an improved stability or an improved turnover, or combinations therefore.
  • oligomerisation is distinct from polymerisation. Oligomers are commonly understood to be molecules containing only a few repeat units, in contrast to polymers, wherein the number of monomeric repeat units is not limited. Dimers, trimers and tetramers are therefore understood to be oligomers.
  • the compounds of formula (I) as defined herein, or catalytic compositions as defined herein are used as oligomerisation catalysts for the preparation of oligomers comprising 2-10 repeat monomeric units.
  • the compounds of formula (I) as defined herein, or catalytic compositions as defined herein are used as oligomerisation catalysts for the preparation of oligomers comprising 2-6 repeat monomeric units. More suitably, the compounds of formula (I) as defined herein, or catalytic compositions as defined herein, are used as oligomerisation catalysts for the preparation of dimers.
  • the compounds of the present invention may be used as an alkene oligomerisation catalyst for the production of alkene oligomers. More specifically, the compounds of the present invention can be used as an alkene oligomerisation catalyst for the selective production of butenes, in particular 1 -butene. [00118] In one embodiment, the compounds of the present invention can be used as alkene dimerisation catalyst.
  • the compounds of the present invention can be used to catalyse the oligomerisation of alkene monomers comprising 2 or more carbons.
  • the compounds and compositions of the present invention can be used to catalyse the oligomerisation of ethene monomers.
  • the compounds of the present invention may be used in the oligomerisation of alkenes.
  • the compounds of the present invention may be used in the oligomiersation of alkene monomers. More suitably, the compounds of the present invention may be used in the dimerisation of alkene monomers. Even more suitably, the compounds of the present invention may be used in the dimerisation of alkene monomers comprising 2 or more carbons.
  • the present invention also provides a process of forming alkene oligomers which comprises reacting alkene monomers in the presence of either:
  • the process may employ a catalytic compositions as defined herein.
  • the catalytic composition comprises a compound of formula I as defined herein and either: (i) a suitable solid support or a suitable activator; or (ii) both a suitable solid support and a suitable activator.
  • the alkene oligomers are prepared by a process of oligomerisation.
  • the alkene monomers are oligomerised to higher order alkene oligomers (e.g. ethene is oligomerised to butene).
  • the mole ratio of suitable activator to compound of formula (I) is 1 :1 to 1 :30.
  • the ratio is 1 :1 to 1 :10. More suitably, the ratio is 1 :1 to 1 :5. Most suitably the ratio is 1 :1 to 1 :2.
  • the process for forming an alkene oligomer proceeds at a temperature of between 0 and 200 °C.
  • the process for forming an alkene oligomer proceeds at a temperature of between 0 and 150 °C. More suitably, the process for forming an alkene oligomer proceeds at a temperature of between 0 and 100 °C. Most suitably, the process for forming an alkene oligomer proceeds at a temperature of between 20 and 100 °C.
  • the process for forming an alkene oligomer proceeds at a temperature of between 40 and 120 °C.
  • the process for forming an alkene oligomer proceeds at a temperature of between 40 and 80 °C. More suitably, the process for forming an alkene oligomer proceeds at a temperature of between 40 and 60 °C.
  • the process for forming an alkene oligomer is performed for a period of 0.5 to 24 hours.
  • the process for forming an alkene oligomer is performed for a period of 5 to 24 hours.
  • the process for forming an alkene oligomer proceeds at a pressure of between 1 and 100 bar.
  • the process for forming an alkene oligomer proceeds at a pressure of between 1 and 50 bar. More suitably, the process for forming an alkene oligomer proceeds at a pressure of between 10 and 50 bar.
  • the process for forming an alkene oligomer proceeds via slurry oligomerisation, wherein the compounds of the present invention are supported on a suitable solid support.
  • the process for forming an alkene oligomer proceeds via a fixed bed reaction, wherein gaseous alkene monomer is passed over the compound of the present invention to produce an alkene oligomer.
  • the alkene monomers are ethylene monomers.
  • the composition used in the process comprises solid MAO as the suitable solid support, wherein the solid support functions as an activator, and, optionally, another activator selected from methylaluminoxane (MAO), polymethylaluminoxane, tri(isobutyl)aluminium (TIBA) or triethylaluminium (TEA).
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TAA triethylaluminium
  • W is tungsten
  • Q is O, 0->LA or N, wherein LA is a Lewis acid and is a dative bond; bond a is either a single bond or double bond;
  • bond b is a multiple bond
  • Ri , R2 and R 3 are independently selected from halo, (1 -6C)alkyl, aryl(1 - 2C)alkyl or OR a , wherein R a is selected from (1 -6C)alkyl, aryl or aryl(1 - 2C)alkyl;
  • Z is a group selected from (1 -6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 , aryl(1 -2C)alkyl or an aryl optionally substituted by one or more groups selected from (1 -6C)alkyl, (3-6C)cycloalkyl, 3- to 6- membered heterocycle, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, C(0)R c , C(0)OR c , OC(0)R c , C(0)N(R b )R c , N(Rb)C(0)R c
  • X is an anionic ligand
  • R d is selected from a (1 -2C)alkyl.
  • cyclopentadienyl pentamethylcyclopentadienyl, indenyl, pentamethylindenyl or (1 -4C)alkoxy.
  • Z is selected from (1 -6C)alkyl, cyclohexyl, SiMe 3 , benzyl, naphthyl or a phenyl, wherein said phenyl is optionally substituted by one or more groups selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , halo, amino, cyano, nitro, carboxy, carbamoyl, sulphamoyl, trifluoromethoxy, haloalkyl, and wherein R b and R c are independently selected from H or (1 - 6C)alkyl.
  • Z is phenyl substituted by one or more groups selected from (2-6C)alkyl, (3- 6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,OR b , NR b R c , aryl, halo or amino, wherein R b and R c are independently selected from H or (1 -6C)alkyl.
  • Z is a group of the formula:
  • R g and Rh are independently selected from (2-6C)alkyl, (3-6C)cycloalkyl, Si[(1 -4C)alkyl] 3 , Si[0(1 -4C)alkyl)] 3 ,ORi, NR,Rj, aryl, halo or amino, wherein Ri and Rj are independently selected from H or (1 -6C)alkyl.
  • a catalytic composition comprising a compound of formula I as defined in any one of paragraph s1 to 15, and either: (i) a suitable solid support or a suitable activator; or (ii) both a suitable solid support and a suitable activator.
  • TMA trimethylaluminium
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TAA triethylaluminium
  • TMA trimethylaluminium
  • MAO methylaluminoxane
  • TIBA tri(isobutyl)aluminium
  • TAA triethylaluminium
  • monomers comprise two or more carbon atoms.
  • catalytic composition comprises a ratio of compound of formula I to activator of between 1 :1 and 1 :30.
  • activator of the catalytic composition comprises an aluminium derivative.
  • TMA trimethylaluminium
  • DMAC dimethyl aluminiumchloride
  • AIMeC ⁇ methylaluminiumdichloride
  • MAO methylaluminoxane
  • polymethylaluminoxane tri(isobutyl)aluminium (TIBA) or triethylaluminium (TEA).
  • suitable solid support of the catalytic composition is also an activator.
  • suitable solid support of the catalytic composition is selected from silica, silica- MAO, polymethylalumioxane, a layered double hydroxide, LDH-MAO, aqueous miscible organic layered double hydroxides (AMO-LDHs), zirconia or titania.
  • Figure 1 shows the conversion of ethylene to 1 - and 2-butenes for varying additive ratios.
  • Figure 2 shows the conversion of ethylene to 1 - and 2-butenes for varying additive ratios, including 1 :2 ratio.
  • Figure 3 shows 1 -butene conversion with variation of additive ratio.
  • Figure 4 shows the products formed over time from the 1 :5 ratio of compound of formula I: additive.
  • Figure 5 shows the percentage conversion of ethylene for varying additive ratios.
  • Figure 6 shows the percentage of ethylene and products vs time for the 1 :5 ratio of compound of formula I: additive.
  • Figure 9 shows the high field regions for 1 H NMR spectra of W(NAr)Cl4(Et 2 0) supported on MgAIC0 3 , showing the formation of 1 -butene (1 .92 and 0.89 ppm), 2-butenes (1 .57 (trans) and 1 .5 (cis) ppm), propylene (1 .54 ppm) and methane (0.16 ppm) in C 6 D 6 at 100 °C from ethylene (1 bar), wherein Ar is 2,6-diisopropylphenyl.
  • Figure 10 shows the high field regions for 1 H NMR spectra of W(NAr)CI 4 (Et 2 0) supported on Si0 2 , showing the formation of 1 -butene (1 .92 and 0.89 ppm), 2-butenes (1 .57 (trans) and 1 .5 (cis) ppm), propylene (1 .54 ppm) and methane (0.16 ppm) in C 6 D 6 at 100 °C from ethylene (1 bar), wherein Ar is 2,6-diisopropylphenyl.
  • Figure 1 1 shows the high field regions for 1 H NMR spectra of W(NAr)Cl4(Et20) supported on polyaluminoxane, showing the formation of 1 -butene (1 .92 and 0.89 ppm), 2-butenes (1 .57 (trans) and 1 .5 (cis) ppm), propylene (1 .54 ppm) and methane (0.16 ppm) in C 6 D 6 at 100 °C from ethylene (1 bar), wherein Ar is 2,6-diisopropylphenyl.
  • Figure 12 shows the high field regions for 1 H NMR spectra of W(NAr)CI 4 (Et 2 0) supported on MgAIS0 4 , showing the formation of 1 -butene (1 .92 and 0.89 ppm), 2-butenes (1 .57 (trans) and 1 .5 (cis) ppm), propylene (1 .54 ppm) and methane (0.16 ppm) in C 6 D 6 at 100 °C from ethylene (1 bar), wherein Ar is 2,6-diisopropylphenyl.
  • Figure 13 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of W(NDipp)CI 4 (Et 2 0) in C 6 D 6 .
  • Figure 14 shows the 13 C CPMAS solid state NMR spectrum of Mg 3 AIN0 3 -W(NDipp)CI 4 .
  • Figure 15 shows the 27 AI NMR spectrum of Mg 3 AIN0 3 -W(NDipp)CI 4 .
  • Figure 16 shows the 13 C CPMAS solid state NMR spectrum of Si0 2 -W(NDipp)CI 4 (THF).
  • Figure 17 shows the 13 C CPMAS solid state NMR spectrum of Mg 3 AIS0 4 - W(NDipp)CI 4 (THF).
  • Figure 18 shows the 27 AI solid state NMR spectrum of Mg 3 AIS0 4 -W(NDipp)CI 4 (THF).
  • Figure 19 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of W(NDipp)Me 3 CI in C 6 D 6 . Resonance at 1 .38 ppm corresponds to silicone grease.
  • Figure 20 shows the 13 C CPMAS solid state NMR spectrum of the complex formed when W(NDipp)CI (THF) is supported on polymethylaluminoxane.
  • Figure 21 shows the 27 AI solid state NMR spectrum of the complex formed when W(NDipp)CI (THF) is supported on polymethylaluminoxane.
  • Figure 22 shows the 13 C CPMAS solid state NMR of the complex formed when W(NDipp)CI 4 (THF) is supported of Mg 3 AIS0 4 -MAO.
  • Figure 23 shows the 27 AI solid state NMR spectrum of the complex formed when W(NDipp)CI 4 (THF) is supported on Mg 3 AIS0 4 -MAO.
  • Figure 26 shows the 13 C CPMAS solid state NMR spectrum of Mg 3 AIS0 4 - W(NDipp)Me 3 CI.
  • Figure 27 shows the 27 AI solid state NMR spectrum of Mg 3 AIS0 4 -W(NDipp)Me 3 CI.
  • Figure 28 shows the molecular structure of W(NMes)CI (THF).
  • Figure 29 shows the ⁇ NMR spectrum of W(NMes)CI 4 (THF) in C 6 D 6 .
  • Figure 30 shows the 1 H NMR spectrum of W(NMes)Me 3 CI in C 6 D 6 , formed from the reaction of W(NMes)CI 4 (THF) and excess trimethylaluminium (-0.3 ppm).
  • Figure 31 shows the molecular structure of W(N(2,6-xylyl))CI 4 (THF).
  • Figure 32 shows the 1 H NMR spectrum of W(N(2,6-xylyl))CI 4 (THF) in C 6 D 6 .
  • Figure 33 shows the molecular structure of W(N(2,6-xylyl))Me 3 CI.
  • Figure 34 shows the 1 H NMR spectrum of W(N(2,6-xylyl))Me 3 CI in C 6 D 6 .
  • Figure 35 shows the molecular structure of W(NPh)CI (THF).
  • Figure 36 shows the 1 H NMR spectrum of W(NPh)CI 4 (THF) in C 6 D 6 .
  • Figure 37 shows the 1 H NMR spectrum of W(NPh)Me 3 CI in C 6 D 6 .
  • Figure 38 shows the molecular structure of W(N(C 6 H 3 F 2 )CI 4 (THF).
  • Figure 39 shows the 1 H NMR spectrum of W(N(C 6 H 3 F 2 )CI 4 (THF) in C 6 D 6 .
  • Figure 40 shows the 1 H NMR spectrum of W(N(C 6 H 3 F 2 ))Me 3 CI in C 6 D 6
  • Figure 41 shows the molecular structure of W(N(C 6 H 4 OMe)CI 4 (THF).
  • Figure 42 shows the ⁇ NMR spectrum of W(N(C 6 H 4 OMe)CI 4 (THF) in C 6 D 6 .
  • Figure 43 shows the molecular structure of W(N(C 6 H 4 OMe)Me 3 CI.
  • Figure 44 shows the ⁇ NMR spectrum of W(N(C 6 H 4 OMe)Me 3 CI in C 6 D 6 .
  • Figure 45 shows the molecular structure of W(N(C 6 H 3 (CF 3 ) 2 ))CI 4 (THF).
  • Figure 46 shows the 1 H NMR spectrum of W(N(C 6 H3(CF3)2))Me 3 CI in C 6 D 6 .Resonance at 0.29 ppm corresponds to silicone grease.
  • Figure 47 shows the turnover numbers for the reaction of W(N(C6H 3 OMe))Me3CI and ethylene 1 bar in C 6 D 6 at 100, 75 and 50 °C.
  • Figure 48 shows a comparison of the poymethylaluminoxane supported W(NDipp)CI 4 (THF) with the silica and LDH supported complexes and the most active homogeneous W:AI mole ratio (1 :2) at 100 °C in C 6 D 6 and 1 bar ethylene.
  • Figure 49 shows the oligomerisation activity of the different W(imido)CU(THF) complexes supported on polymethylaluminoxane in C 6 D 6 at 100 °C and 1 bar ethylene.
  • Figure 50 shows the oligomerisation activity of the polymethylaluminoxane supported W(N(C 6 H 3 OMe))CI 4 (THF) complex at 100, 75 and 50 °C in C 6 D 6 and 1 bar ethylene.
  • Figure 51 shows the turnover number (TON) over time for the varying W:MAO ratios.
  • [W(NDipp)Me 3 CI] 4.55 ⁇ .
  • Figure 52 shows the percentage selectivity for 1 -butene over time for the varying W:MAO ratios.
  • [W(NDipp)Me 3 CI] 4.55 ⁇ .
  • NMR spectra were measured on a 400 MHz Bruker Avance III HD NanoBay spectrometer. 1 H and 13 C ⁇ 1 H ⁇ NMR spectra were recorded at 25 °C and referenced internally to the residual protio-solvent resonance of the deuterated solvent used. 1 H and 13 C ⁇ 1 H ⁇ chemical shifts, ⁇ , are given in parts per million (ppm).
  • GC-MS were recorded on an Agilent Technologies 7820A GC system equipped with a PLOT column (27.5 m x 0.32 mm x 5 ⁇ ), coupled to an Agilent Technologies 5977E MSD instrument
  • LDH-MAO layered double hydroxides
  • a variety of polymethylaluminoxane supports can be used in this synthesis.
  • An exemplary solid MAO is prepared by an adaptation of the optimised procedure in Kaji et al. in the US 8,404,880 B2 embodiment 1 (Scheme 1 ).
  • each synthesised solid MAO is represented as solid MAO(Step 1 Al:0 ratio/Step 2 temperature in ⁇ time in h/Step 3 temperature in °C,time in h).
  • the synthesis conditions outlined in Scheme 1 would yield solid MAO(1 .2/70,32/100,12).
  • the mixture obtained was a colourless solution free of gelatinous material, which was subsequently heated at 100 °C for 12 h.
  • the reaction mixture was cooled to room temperature and hexane (40 mL) added, resulting in the precipitation of a white solid which was isolated by filtration, washed with hexane (2 x 40 mL) and dried in vacuo for 3 h.
  • Total yield 1 .399 g (71 % based on 40 wt% Al).
  • the supported complex (5 mg) was added to a Young's tap NMR tube, along with MAO if required, and dissolved in C 6 D 6 (500 mg). The internal standard was added and the tube freeze-pump-thaw degassed three times. Ethylene (1 bar) was added and the run started.
  • Table 1 the conversion of ethylene to 1- and 2-butenes for varying complex: MAO ratios at 100 V and 1 bar ethylene pressure.
  • Table 3 the ercentage conversion of ethylene to butenes for varying activator ratios.
  • Table 7 the ratio of products formed (1-butene, cis-2-butene and trans-2-butene) with varying cocatalyst ratios by 1 H NMR spectroscopy and GCMS analysis.
  • W(NAr)CI 4 (Et20) was supported on polymethylaluminoxane (thus forming the proposed W(NAr)Me 3 CI) and the oligomerisation was carried out as described above.
  • Table 9 the ratio of products (1-butene, cis-2-butene and trans-2-butene) from the reaction of W(NAr)CI 4 (Et 2 0) supported on polyaluminoxane with ethylene at 75, 50 and
  • Figures 13 to 18 show the complex W(NDipp)CI 4 (Et 2 0) (wherein 'Dipp' denotes 2,6-diisopropylphenyl) supported on the surface of Layered Double Hydroxides and silica resulting in the proposed species W(NDipp)CI 3 being bound to surface oxygen atoms.
  • 'Dipp' denotes 2,6-diisopropylphenyl
  • silica resulting in the proposed species W(NDipp)CI 3 being bound to surface oxygen atoms.
  • 13 C NMR spectral resonances in the region 120-160 ppm correspond to aromatic carbon environments and 10-30 the isopropyl groups.
  • 27 AI spectral resonances for LDHs show the bulk aluminium environment ( ⁇ 8 ppm) along with the surface aluminium sites ( « 77 ppm).
  • FIG. 19 to 27 collectively show that when W(NDipp)CI 4 (Et 2 0) is supported on a methylaluminium-containing support material (e.g. polymethylaluminoxane or LDH- MAO), the W(NDipp)CU(Et20) species undergoes reaction with the methylaluminium species, resulting in the postulated formation of the corresponding trimethyl complex (e.g. W(NDipp)Me 3 CI) on the surface of the support material.
  • a methylaluminium-containing support material e.g. polymethylaluminoxane or LDH- MAO
  • the W(NDipp)CU(Et20) species undergoes reaction with the methylaluminium species, resulting in the postulated formation of the corresponding trimethyl complex (e.g. W(NDipp)Me 3 CI) on the surface of the support material.
  • the corresponding trimethyl complex e.g. W(NDipp)Me 3
  • Figures 28 to 46 show the tungsten imido complexes synthesised during this study, including molecular structures and 1 H NMR spectroscopy.
  • Another compound used in this study is W(NDipp)CU(THF) (wherein 'Dipp' denotes 2,6-diisopropylphenyl).
  • the general synthetic method used to prepare these compounds is as follows: The relevant isocyanate RNCO is reacted with W(0)CU in octane at reflux for 16 hours.
  • the compounds e.g. W(NR)CU
  • W(NR)CI 4 (THF) can be recrystallized from THF or Et 2 0 as the adduct (e.g. W(NR)CI 4 (THF)).
  • TMA trimethylaluminium
  • LDH-MAO was prepared by reacting 2 equivalents of LDH to one equivalent of MAO in toluene at 80 °C for 2 hours. The resulting suspension was filtered and dried to yield a white solid. Polymethylaluminoxane was synthesised as described hereinbefore.
  • W(NDipp)CI 4 (Et 2 0) by weight was reacted with the chosen support in toluene.
  • W(NDipp)CI 4 (Et 2 0) (10 mg, 17.4 ⁇ )
  • Mg 3 AIS0 4 (200 mg) were charged in separate schlenks.
  • Toluene (-20 ml) was added to both and the green complex solution filtered across.
  • the resulting suspension was swirled intermittently for one hour. Immediate decolouration of the green solution was observed and the colourless support became orange. After one hour the solution was completely clear and colourless at which point it was filtered off.
  • Figure 47 shows homogeneous oligomerisation of ethylene (1 bar) using W(N(C 6 H 4 OMe))Me3CI (depicted in Figure 43) at various temperatures.
  • W(N(C6H 4 OMe))Me3CI is an effective ethylene oligomerisation catalyst at temperatures ranging from 50-100°C, in particular towards the lower end of this range.
  • Figure 48 and Table 10 below compares the ability of various supported and unsupported W(NDipp)CI (THF) catalysts to catalyse the oligomerisation of ethylene.
  • Fig. 48 shows that the catalytic composition afforded when W(NDipp)CI (THF) is supported on polymethylaluminoxane is noticeably more active than the unsupported complex ('homogeneous 1 :2') and the silica- and LDH-supported complexes.
  • figure 48 shows that when polymethylaluminoxane is used as the support material, the oligomerisation of ethylene is up to 7 times that seen for homogeneous reaction (i.e. unsupported W(NDipp)CI 4 (THF)).
  • Figure 49 compares the ability of various polymethylaluminoxane-supported tungsten imido complexes to catalyse the oligomerisation of ethylene.
  • Figure 49 shows that the catalytic composition afforded when W(NC 6 H 3 (3,5- CF 3 ))CI 4 (THF) is supported on polymethylaluminoxane is up to 12 times more catalytically active than the catalytic composition afforded when W(N2,6-xylyl)CI 4 (THF) is supported on polymethylaluminoxane, which suggests that the electronic effect of the imido group has a strong influence on the catalytic characteristics.
  • Figure 50 shows heterogeneous oligomerisation of ethylene using the complex afforded when W(N(C 6 H 4 OMe))CI (THF) is supported on polymethylaluminoxane at various temperatures. The data show that the highest turnover is achieved when the oligomerisation reaction is conducted at 50 °C.
  • Table 1 1 shows the catalytic properties of the complex formed when W(0)CU (not a compound of the invention) is supported on solid MAO.
  • Table 1 1. Turnover numbers for W(0)CU supported on polymethylaluminoxane at 100 V in C 6 D 6 and 1 bar ethylene.

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Abstract

L'invention concerne de nouveaux composés contenant du tungstène de formule I tels que définis dans la description, ainsi que des compositions catalytiques comprenant les composés. L'invention concerne également des utilisations des composés et des compositions dans des réactions d'oligomérisation d'alcènes.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3140775A1 (fr) * 2022-10-17 2024-04-19 IFP Energies Nouvelles Nouvelle composition catalytique à base de chrome ou de titane supporté

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5639900A (en) * 1993-12-29 1997-06-17 Metton America, Inc. Thermally activated olefin metathesis catalyst precursor
EP0846705A2 (fr) * 1992-07-01 1998-06-10 Exxon Chemical Patents Inc. Précurseurs de catalyseurs à base de métal de transition des groupes 5 et 6
WO2012092014A2 (fr) * 2010-12-29 2012-07-05 Uop Llc Procédé de métathèse d'oléfines et catalyseur contenant des liaisons tungstène-fluor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0846705A2 (fr) * 1992-07-01 1998-06-10 Exxon Chemical Patents Inc. Précurseurs de catalyseurs à base de métal de transition des groupes 5 et 6
US5639900A (en) * 1993-12-29 1997-06-17 Metton America, Inc. Thermally activated olefin metathesis catalyst precursor
WO2012092014A2 (fr) * 2010-12-29 2012-07-05 Uop Llc Procédé de métathèse d'oléfines et catalyseur contenant des liaisons tungstène-fluor

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SCHROCK, R. S. ET AL: "Controlled ring-opening metathesis polymerization by molybdenum and tungsten alkylidene complexes", XP002758905, retrieved from STN Database accession no. 1989:554417 *
ERALD FELDMAN ET AL: "Preparation and reactivity of Tungsten(VI) metallacyclobutane complexes. Square pyramids versus trigonal bipyramids", ORGANOMETALLICS, vol. 9, no. 9, 1990, American Chemical Society, pages 2535 - 2548, XP002758907, ISSN: 0276-7333 *
OLIVIER H ET AL: "Homogeneous and two-phase dimerization of olefins catalyzed by tungsten complexes. The role of imido ligands and Lewis acids", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 148, no. 1-2, 1 December 1999 (1999-12-01), pages 43 - 48, XP002351888, ISSN: 1381-1169, DOI: 10.1016/S1381-1169(99)00056-4 *
S. TOBISCH: "Stable Lewis acid chelate of a bis(imido) tungsten compound and implications for alpha-olefin dimerisation products : a DFT study", DALTON TRANSACTIONS, 2008, GBCHEMICAL SOCIETY. LETCHWORTH., pages 2120 - 2127, XP002758906, ISSN: 0300-922X *
SCHROCK, R. S. ET AL: "Controlled ring-opening metathesis polymerization by molybdenum and tungsten alkylidene complexes", REPORT , TR-2; ORDER NO. AD-A198073, 32 PP. AVAIL.: NTIS FROM: GOV. REP. ANNOUNCE. INDEX (U. S.) 1989, 89(1), ABSTR. NO. 900,563, 1988 *
STEVEN F PEDERSEN ET AL: "Preparation of tungsten(VI) phenylimido alkyl and alkylidene complexes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, US, vol. 104, no. 26, 1 January 1982 (1982-01-01), pages 7483 - 7491, XP002580510, ISSN: 0002-7863, DOI: 10.1021/JA00390A016 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3140775A1 (fr) * 2022-10-17 2024-04-19 IFP Energies Nouvelles Nouvelle composition catalytique à base de chrome ou de titane supporté
WO2024083616A1 (fr) * 2022-10-17 2024-04-25 IFP Energies Nouvelles Nouvelle composition catalytique à base de chrome ou de titane supporté

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