Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts
View Patent ↗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.
1. A compound that is a metal ligand complex characterized by the general formula:
wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 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 proviso that R 1 may not be hydrogen, and optionally two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
X 1 is C, X 2 is O, S, N or CR 5 , X 3 is O, S, N or CR 6 , and X 4 is CR 7 , provided that the heteroatom containing ring system is heteroaromatic, and provided that when X 2 is S, R 7 is aryl;
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 2, the complex being a bis-ligand complex comprising a first phenol-heterocycle ligand and a second phenol-heterocycle ligand, wherein the first and second phenol-heterocycle ligands are different from the other; and
m″ is 0, 1, 2, 3, or 4.
2. The compound of claim 1 , wherein the metal ligand complex is characterized by a formula selected from the group consisting of
3. The compound of either of claims 1 or 2 , wherein R 1 is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl.
4. The compound of either of claims 1 or 2 , wherein R 7 is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl.
5. The compound of claim 4 , wherein R 1 is selected from the group consisting of t-butyl, naphthyl, substituted naphthyl, N-carbazolyl, substituted N-carbazolyl, phenyl and substituted phenyl and R 7 is selected from the group consisting of substituted phenyl and anthracenyl.
6. A metal-ligand complex that is characterized by the general formula:
wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 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 proviso that R 1 may not be hydrogen, optionally two or more of R 1 , R 2 , R 3 and R 4 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 R 5 , R 6 and R 7 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;
X 1 is N or C, X 2 is O, S, N(R 5 ) n′ or CR 5 , X 3 is O, S, N(R 6 ) n″ or CR 6 , X 4 is O, S, N(R 7 ) n′″ or CR 7 , wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic;
X 5 is N or C, X 6 is O, S, N(R 5 ) n′ or CR 5 , X 7 is O, S, N(R 6 ) n″ or CR 6 , X 8 is O, S, N(R 7 ) n′″ or CR 7 , 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 X 1 , X 2 , X 3 , X 4 , N ring are different from the atoms in the X 5 , X 6 , X 7 , X 8 , N ring in the selection of the C, N, O or S atom, such that at least, either X 1 and X 5 are different or X 2 and X 6 are different or X 3 and X 7 are different or X 4 and X 8 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.
7. A metal ligand complex characterized by the general formula:
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 and R 11 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 proviso that R 1 may not be hydrogen, optionally two or more of R 1 , R 2 , R 3 and R 4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R 8 , R 9 , R 10 and R 11 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;
X 1 is N or C, X 2 is O, S, N(R 5 ) n′ or CR 5 , wherein n′ is 0 or 1, provided that the heteroatom containing ring system is heteroaromatic, provided X 1 and X 2 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 2, forming a bis-ligand complex comprising a first phenol-heterocycle ligand and a second phenol-heterocycle ligand, wherein the first and second phenol-heterocycle ligands are different from the other; and,
m″ is 0, 1, 2, 3, or 4.
8. The complex of claim 7 , wherein the complex is characterized by a formula selected from the group consisting of:
9. The complex of either of claims 7 or 8 , wherein R 1 is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl, and heteroaryl.
10. The complex of any of claims 1 , 2 , 7 or 8 wherein M is either Zr, Hf or Ti.