Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
View Patent ↗New ligands, compositions, metal-ligand complexes and arrays with bridged bis-aromatic ligands are disclosed that catalyze the polymerization of monomers into polymers. These catalysts with metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, propylene or styrene. The catalysts also polymerize propylene into isotactic polypropylene.
1. A metal complex having two seven-member metallocycles, wherein each metallocycle includes four atoms from a bis-aromatic moiety and is formed with bonds from the metal atom to heteroatoms selected from the group consisting of oxygen and sulfur, and wherein said two seven-member metallocycles are joined together by one bridging group and wherein the metal in said metal complex is selected from the group consisting of groups 3–6 and Lanthanide elements of the Periodic Table of Elements.
2. The metal complex of claim 1 , wherein said two, bridged seven-member metallocycles are compositionally identical.
3. The metal complex of claim 2 , wherein each of said metallocycles includes four atoms from a bis-aryl moiety.
4. A metal complex characterized by the general formula:
(4,2,O,S)ML n′
where (4,2,O,S) is a dianionic ligand having at least 4 atoms that are oxygen or sulfur and chelating to the metal M at at least 2 coordination sites through covalent bonds from either oxygen or sulfur atoms to M; M is a metal selected from the group consisting of groups 3–6 and Lanthanide elements of the Periodic Table of Elements; each L is the same or different from the others and in each case is a moiety bonded to the metal M with a covalent, dative or ionic bond; and n′ is 1, 2, 3, or 4.
5. The metal complex of claim 4 , wherein each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, amine, hydrido, allyl, diene, phosphino, phosphine, carboxylates, alkylthio, arylthio, thioxy, 1,3-dionate, oxalate, carbonate, nitrate, and sulphate.
6. The composition of claim 4 , wherein at least one L is an anion.
7. A metal complex characterized by either of the general formulas:
wherein at least two of the bonds to M are covalent, with the other bonds being dative; and each AR is an aromatic group that can be the same or different from the other AR groups with each AR being independently selected from the group consisting of optionally substituted aryl or heteroaryl; B is a bridging group having from one to 50 atoms not counting hydrogen atoms; X and X′ are the same or different and are independently selected from the group consisting of oxygen, sulfur, and —PR 30 —, where R 30 is selected from the group consisting of hydride, halide, and optionally substituted hydrocarbyl, heteroatom-containing hydrocarbyl, silyl, boryl, alkoxy, or aryloxy; when the bond to M is covalent Y 2 and Y 3 and X 4 and X 5 are the same or different and are independently selected from the group consisting of oxygen, sulfur, —NR 30 —, and —PR 30 —, where R 30 is defined above; when the bond to M is dative Y 2 and Y 3 and X 4 and X 5 are the same or different and are independently selected from the group consisting of optionally substituted amino, phosphino, hydroxy, alkoxy, aryloky, thioxy, alkylthio and arylthio;
M is a metal selected from groups 3–6 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 or 4.
8. The complex of claim 7 wherein the complex is characterized by the general formula:
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 is independently selected from the group consisting of hydride, halide, and optionally substituted hydrocarbyl, heteroatom-containing hydrocarbyl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, thioxy, seleno, or nitro; optionally two or more R groups can combine together into ring structures, with such ring structures having from 3 to 100 atoms in the ring not counting hydrogen atoms.
9. The complex of claim 8 wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 is independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, alkylthio, arylthio, thioxy, seleno, or nitro.
10. The complex of claim 9 , wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 is independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, amino, alkylthio, arylthio or thioxy.
11. The complex of claim 8 wherein the complex is characterized by the general formula:
wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are as defined above, B is as defined above, X and X′ are as defined above, and Y 2 and Y 3 are as defined above; and M, L and n′ are as defined above.
12. The complex of claim 11 , wherein the complex is characterized by the formula:
wherein each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently selected from the group consisting of hydride, halide, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, alkylthio, arylthio, thioxy, seleno, or nitro; and M, Y 2 , L and n′ are as defined above.
13. The complex of either of claims 8 , 9 , 10 , 11 , or 12 , wherein at least one of R 2 and R 12 is not hydrogen.
14. The composition of claim 13 , wherein R 2 and R 12 are independently selected from the group consisting of optionally substituted aryl and heteroaryl.
15. The complex of claim 7 , 8 , 9 , 10 , 11 , or 12 , wherein the bridging group B is selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent heteroatom containing hydrocarbyl.
16. The complex of claim 15 , wherein B is selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.
17. The complex of claim 15 , wherein B is represented by the general formula —(Q″R 40 2-z″ ) z′ — wherein each Q″ is either carbon or silicon and each R 40 may be the same or different from the others such that each R 40 is selected from the group consisting of hydride and optionally substituted hydrocarbyl, and optionally two or more R 40 groups may be joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z′ is an integer from 1 to 10; and z″ is 0, 1 or 2.
18. The metal complex either of claim 7 , 8 , 9 , 10 , 11 , or 12 , wherein each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, amine, hydrido, allyl, diene, phosphino, phosphine, carboxylates, alkylthio, arylthio, thioxy, 1,3-dionate, oxalate, carbonate, nitrate, sulphate.
19. The complex of either of claim 7 , 8 , 9 , 10 , 11 , or 12 , wherein at least one L is an anion.
20. The complex of claim 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , or 12 , wherein M is selected from the group consisting of Hf, Zr and Ti.