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 metal complex characterized by the general formula:
wherein at least two of the bonds from Y 2 , Y 3 , X and X′ to M are covalent, with the other bonds being dative; 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 and heteroaryl; B is a bridging group having from two to 50 atoms not counting hydrogen atoms and is selected from the group consisting of substituted divalent hydrocarbyl and divalent heteroatom-containing hydrocarbyl; X and X′ are independently selected from the group consisting of oxygen, sulfur, —P(R 30 ) r —, and optionally substituted alkoxy, aryloxy, alkylthio, arylthio; Y 2 and Y 3 are independently selected from the group consisting of oxygen, sulfur, —N(R 30 ) r —, —P(R 30 ) r —, and optionally substituted alkoxy, aryloxy, alkylthio, or arylthio, where R 30 is selected from the group consisting of hydrogen, halogen, and optionally substituted hydrocarbyl, heteroatom-containing hydrocarbyl, silyl, boryl, alkoxy, or aryloxy and r is 0 or 1;
M is a metal selected from groups 3–6 and lanthanide elements of the periodic table of elements;
each L is independently a moiety that forms a covalent dative or ionic bond with M; and n′ is 1, 2, 3 or 4.
2. The complex of claim 1 , wherein B is selected from the group consisting of substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.
3. The complex of claim 1 , wherein the bridging group B is substituted with one or more optionally substituted hyrocarbyl or heteroatom-containing hydrocarbyl groups, not counting AR—X and AR—X′.
4. The complex of claim 1 , wherein the bridging group B is substituted with two or more hydrocarbyl or heteroatom-containing hydrocarbyl groups, not counting AR—X and AR—X′, wherein two or more of the hydrocarbyl or heteroatom-containing hydrocarbyl groups are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms.
5. The complex of claim 1 , wherein:
the bridging group B includes a bridge of one or more atoms extending from X to X′, the bridge including one or more atoms adjacent to the X and/or the X′; and
one or more of the bridge atoms adjacent to one or more of the X and/or the X′ is bonded to one or more substituents, not counting bonds to X and/or X′ or neighboring atoms along the bridge, the one or more substitutents being independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl.
6. The complex of claim 1 , wherein the bridging group B is substituted with a plurality of substitutents independently selected from the group consisting of optionally substituted alky, heteroalkyl, aryl and heteroaryl, each of the bridge atoms adjacent to the X and/or the X′ being bonded to at least one of the plurality of substituents, not counting bonds to X and/or X′ or neighboring atoms along the bridge, wherein two or more of the substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms.
7. The complex of claim 6 , wherein each of the bridge atoms adjacent to the X and/or the X′ is bonded to two of the plurality of substituents.
8. The complex of claim 1 , wherein the group X—B—X′ is selected from the group consisting of
wherein each Q is independently selected from the group consisting of carbon and silicon, each R 60 is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, provided that at least one R 60 substituent is not hydrogen, wherein the R 60 substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and m′ is 0, 1, or 2.
9. The complex of claim 8 , wherein the group X—B—X′ is selected from the group consisting of X—CH(CH 3 )—CH(CH 3 )—X′, X—CH 2 —CH(CH 3 )—CH 2 —X′, X—CH 2 —C(CH 3 ) 2 —CH 2 —X′, X—CH 2 —CH(C 6 H 5 )—CH 2 —X′, X—CH(CH 3 )—CH 2 —CH(CH 3 )—X′, X—CH(CH 2 H 5 )—CH 2 —CH(C 2 H 5 )—X′, X—CH(CH 3 )CH 2 CH 2 CH(CH 3 )—X′, X—CH(C 6 H 5 )CH 2 CH(C 6 C 5 )—X′,
10. The complex of claim 1 , wherein B is represented by the general formula (Q″R 40 Z-z″ ) z′ — wherein each Q″ is independently either carbon or silicon and wherein each R 40 substituent is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl or heteroatom containing hydrocarbyl, provided that at least one R 40 substituent is not hydrogen, wherein two or more 40 substituents are optionally 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.
11. The complex of claim 9 , wherein z′ is an integer greater than 1, and two or more R 40 substituents are independently selected from the group consisting of optionally substituted hydrocarbyl and heteroatom-containing hydrocarbyl.
12. The complex of claim 9 , wherein z′ is an integer greater than 1, and the bridging group B is substituted such that one or more of the R 40 substituents bonded to a Q″ adjacent to one or more of X and X′ is independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl.
13. The complex of claim 9 , wherein the bridging group B is substituted such that a plurality of R 40 substitutents are independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, alkyl and heteroaryl, each Q″ adjacent to the X and or the X′ being bonded to at least one of the plurality of R 40 substituents.
14. The complex of claim 9 , wherein each Q″adjacent to the X and/or the X′is bonded to two of the plurality of R 40 substituents.
15. The complex of claim 1 , wherein the metal complex includes one or more chiral centers.
16. The complex of claim 15 , wherein the bridging group B includes at least one chiral center.
17. The complex of claim 15 , wherein the metal complex can be formed into enantiomeric or diastereomeric forms.
18. A metal complex characterized by the general 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 hydrogen, halogen, nitro, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl phosphino, amino, alkylthio, or arylthio; and
wherein at least two of the bonds from Y 2 , Y 3 , X and X′ to M are covalent, with the other bonds being dative; B is a bridging group having from two to 50 atoms not counting hydrogen atoms and is selected from the group consisting of substituted divalent hydrocarbyl and divalent heteroatom-containing hydrocarbyl; X and X′ are independently selected from the group consisting of oxygen, sulfur, —P(R 30 ) r —, and optionally substituted alkoxy, aryloxy, alkylthio, arylthio; Y 2 and Y 3 are independently selected from the group consisting of oxygen, sulfur, —N(R 30 ) r —, —P(R 30 ) r —, and optionally substituted alkoxy, aryloxy, alkylthio, or arylthio, where R 30 is selected from the group consisting of hydrogen, halogen, and optionally substituted hydrocarbyl, heteroatom-containing hydrocarbyl, silyl, boryl, alkoxy, or aryloxy, and r is 0 or 1;
M is a metal selected from groups 3–6 and lanthanide elements of the periodic table of elements;
each L is independently a moiety that forms a covalent, dative or ionic bond with M; and n′ is 1, 2, 3 or 4.
19. The complex of claim 18 , wherein B is selected from the group consisting of substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.
20. The complex of claim 18 , wherein:
the bridging group B includes a bridge of one or more atoms extending from X to X′, the bridge including one or more atoms adjacent to the X and/or the X′; and
one or more of the bridge atoms adjacent to one or more of the X and/or the X′ is bonded to one or more substituents, not counting bonds to X and/or X′ or neighboring atoms along the bridge, the one or more substitutents being independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl.
21. The complex of claim 18 , wherein the bridging group B is substituted with a plurality of substitutents independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl, each of the bridge atoms adjacent to the X and/or the X′ being bonded to at least one of the plurality of substituents, not counting bonds to X and/or X′ or neighboring atoms along the bridge, wherein two or more of the substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms.
22. The complex of claim 18 , wherein the group X—B—X′ is selected from the group consisting of
wherein each Q is independently selected from the group consisting of carbon and silicon, each R 60 is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl or heteroatom containing hydrocarbyl, provided that at least one R 60 substituent is not hydrogen, wherein the R 60 substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and m′ is 0, 1, or 2.
23. The complex of claim 18 , wherein the bridging group B includes one or more chiral centers.
24. The complex of claim 18 , wherein X—B—X′ is characterized by the formula
and at least one R 60 group is not hydrogen or at least one R 60 group on each Q is not hydrogen.
25. The complex of claim 18 , wherein the group X—B—X′ is selected from the group consisting of X—CH(CH 3 )—CH(CH 3 )—X′, X—CH 2 —CH(CH 3 )—CH 2 —X′, X—CH 2 —C(CH 3 ) 2 —CH 2 —X′, X—CH 2 —CH(C 6 H 5 )—CH 2 —X′, X—CH(CH 3 )—CH 2 —CH(CH 3 )—X′, X—CH 2 —(C 2 H 5 )—CH 2 —CH(C 2 H 5 )—X′, X—CH(CH 3 )CH 2 CH 2 CH(CH 3 X′, X—CH(C 6 H 5 )CH 2 CH(C 6 H 5 )—X′,