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US 2006/0135713 A1Published application
Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts
AssigneeSymyx Solutions, Inc.
InventorsMargarete Leclerc, Xiaohong Bei, James Longmire, Gary Diamond, James Shoemaker, Anne LaPointe, Lily Ackerman
Life of this patent
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Abstract
Ligands, compositions, and metal-ligand complexes that incorporate phenol-heterocyclic compounds are disclosed that are useful in the catalysis of transformations such as the polymerization of monomers into polymers. The catalysts have high performance characteristics, including high comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, propylene or styrene. The catalysts particularly polymerize styrene to form polystyrene.
Claims35
A compound that is a metal ligand complex characterized by the general formula:
- wherein each R1, R2, R3, R4, R5, R6, R7 are the same or different and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R5, R6 and R7 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
- X1 is N or C, X2 is O, S, N(R5)n′ or CR5, X3 is O, S, N(R6)n″ or CR6, X4 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
- provided combinations of X1, X2;
- X1, X3;
- and X1, X4 are not both N and X1, X2 and X3 are not all N;
- further provided where X1, X3, X4 are each N, X2 is C, R5 is H and R1 is selected from the group consisting of t-butyl, —CMe2Et, —C(Et)3, —CMe2Ph, —C(Ph)3, —Si(Et)3, and —Si(Ph)3, and when R1 is F, R3 is F, X1, X2, X3 are all C, X4 is N, R5, R6 are each H and R7 is t-butyl are not included;
- wherein M is a metal selected from the group consisting of groups 3 through 6 of the periodic table elements and lanthanides;
- wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof;
- x is 1, 2, 3, or 4;
- and
- m″ is 0, 1, 2, 3, or 4.
8 more elements
A metal-ligand complex that is characterized by the general formula:
- wherein each R1, R2, R3, R4, R5, R6, R7 are the same or different and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 on the same ring in the formula may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R5, R6 and R7 on the same ring in the formula may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
- X1 is N or C, X2 is O, S, N(R5)n′ or CR5, X3 is O, S, N(R6)n″ or CR6, X4 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
- X5 is N or C, X6 is O, S, N(R5)n′ or CR5, X7 is O, S, N(R6)n″ or CR6, X8 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
- further provided that the atoms in the X1, X2, X3, X4, N ring are different from the atoms in the X5, X6, X7, X8, N ring in the selection of the C, N, O or S atom, such that at least, either X1 and X5 are different or X2 and X6 are different or X3 and X7 are different or X4 and X8 are different;
- wherein M is a metal selected from the group consisting of groups 3 through 6 of the periodic table elements and lanthanides;
- wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof;
- and
- m″ is 0, 1, 2, or 3.
5 more elements
A metal ligand complex characterized by the general formula:
- wherein R1, R2, R3, R4, R5, R8, R9, R10 and R11 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R8, R9, R10 and R11 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
- X1 is N or C, X2 is O, S, N(R5)n′ or CR5, wherein n′ is 0 or 1, provided that the heteroatom containing ring system is heteroaromatic, provided X1 and X2 are not both N;
- wherein M is a metal selected from the group consisting of groups 3 through 6 of the periodic table of elements and lanthanides;
- wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof;
- x is 1, 2, 3, or 4;
- m″ is 0, 1, 2, 3, or 4.
3 more elements
A composition comprising:
- a) a compound characterized by the general formula:
- wherein R1, R2, R3, R4, R5, R6, R7 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R5, R6 and R7 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
- X1 is N or C, X2 is O, S, N(R5)n′ or CR5, X3 is O, S, N(R6)n″ or CR6, X4 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
- provided combinations of X1, X2;
- X1, X3;
- and X1, X4 are not both N and X1, X2 and X3 are not all N;
- and
- further provided compounds where X1, X3, X4 are each N, X2 is C, R5 is H and R1 is selected from the group consisting of t-butyl, —CMe2Et, —C(Et)3, —CMe2Ph, —C(Ph)3, —Si(Et)3, and —Si(Ph)3;
- and when R1 is F, R3 is F, X1, X2, X3 are all C, X4 is N, R5, R6 are each H and R7 is t-butyl are not included;
- and
- b) a metal precursor characterized by the general formula M(L)n where M is a metal selected from groups 3-6 of the periodic table of elements and lanthanide elements of the periodic table of elements, each L is a moiety that forms a covalent, dative or ionic bond with M;
- and n is 1, 2, 3, 4, 5, or 6
9 more elements
A composition comprising:
- a) a compound characterized by the general formula:
- wherein R1, R2, R3, R4, R5, R8, R9, R10, and R11 are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R8, R9, R10 and R11 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
- and
- X1 is N or C, X2 is O, S, N(R5)n′ or CR5, wherein n′ is 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
- and
- provided X1 and X2 are not both N.;
- and
- b) a metal precursor characterized by the general formula M(L)n where M is a metal selected from groups 3-6 of the periodic table of elements and lanthanide elements of the periodic table of elements, each L is a moiety that forms a covalent, dative or ionic bond with M;
- and n is 1, 2, 3, 4, 5, or 6
6 more elements
Dependencies are inferred from the claim text.