Bridged bi-aromatic catalysts, complexes, and methods of using the same
View Patent ↗Ligands, compositions, metal-ligand complexes and arrays with substituted bridged bis-biaromatic ligands, and methods of making and using the same, 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 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 catalyst, comprising:
a metal complex characterized by either of the general formulas:
wherein at least two of the bonds to M are covalent, when the bond to M is covalent Y 2 and Y 3 and X and X′ are the same or different and independently selected from the group consisting of oxygen, sulfur, —NR 30 —, 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, and aryloxy; when the bond to M is dative Y 2 and Y 3 and X and X′ are the same or different and independently selected from the group consisting of optionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy, thioxy, alkylthio and arylthio;
each of R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , 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, nitro, and combinations thereof; 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;
each of R 4 and R 14 is independently selected from the group consisting of halide, and optionally substituted alkoxy, aryloxy, phosphino, amino, alkylthio, arylthio, and thioxy;
B is a bridging group having from one to 50 atoms not counting hydrogen atoms;
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; and
one or more activators.
2. A catalyst, comprising:
a metal complex characterized by either of the general formulas:
wherein at least two of the bonds to M are covalent, when the bond to M is covalent Y 2 and Y 3 X and X′ are the same or different and independently selected from the group consisting of oxygen, sulfur, —NR 30 —, 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, and aryloxy; when the bond to M is dative Y 2 and Y 3 and X and X′ are the same or different and independently selected from the group consisting of optionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy, thioxy, alkylthio and arylthio;
each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , 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, nitro, and combinations thereof; 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;
each of R 7 and R 17 is independently selected from the group consisting of halide, and optionally substituted alkoxy, aryloxy, phosphino, amino, alkylthio, arylthio, and thioxy;
B is a bridging group having from one to 50 atoms not counting hydrogen atoms;
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; and
one or more activators.
3. A catalyst, comprising:
a metal complex characterized by either of the general formulas:
wherein at least two of the bonds to M are covalent, when the bond to M is covalent Y 2 and Y 3 and X and X′ are the same or different and independently selected from the group consisting of oxygen, sulfur, —NR 30 —, 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, and aryloxy; when the bond to M is dative Y 2 and Y 3 and X and X′ are the same or different and independently selected from the group consisting of optionally substituted amino, phosphino, hydroxy, alkoxy, aryloxy, thioxy, alkylthio and arylthio;
each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , 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, nitro, and combinations thereof; 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;
each of R 7 and R 17 is independently selected from the group consisting of halide, and optionally substituted alkoxy, aryloxy, phosphino, amino, alkylthio, arylthio, and thioxy;
B is a bridging group having from one to 50 atoms not counting hydrogen atoms;
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; and
one or more activators.
4. The catalyst of any one of claims 1 , 2 and 3 , 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.
5. The catalyst of claim 4 , wherein the complex is characterized by the formula:
wherein each of R 2 , R 3 , R 5 , R 6 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, and nitro; and B, R 4 , R 7 , R 8 , M, Y 2 , L and n′ are as defined above.
6. The catalyst of claim 5 , wherein each X and Y 2 is independently selected from the group consisting of oxygen and sulfur.
7. The catalyst of claim 5 , further comprising a support selected from the group consisting of silicas, aluminas, clays, zeolites, magnesium chloride, polystyrenes, and substituted polystyrenes.
8. The catalyst of claim 5 , wherein each R 2 is independently selected from the group consisting of optionally substituted aryl and heteroaryl.
9. The catalyst of claim 5 , wherein the bridging group B is selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent heteroatom containing hydrocarbyl.
10. The catalyst of claim 9 , wherein B is selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.
11. The catalyst of claim 9 , 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.
12. The catalyst of claim 5 , wherein at least one L is an anion.
13. The catalyst of claim 5 , wherein M is selected from the group consisting of Hf, Zr and Ti.