Quinolinyldiamido transition metal complexes, production and use thereof

1. A quinolinyldiamido transition metal complex represented by Formula I:

wherein:

M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;

J is a three-atom-length bridge between the quinoline and the amido nitrogen;

X is an anionic leaving group;

L is a neutral Lewis base;

R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;

R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;

n is 1 or 2;

m is 0, 1, or 2

n+m is not greater than 4; and

any two adjacent R groups (e.g., R 1 & R 2 , R 2 & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;

any two X groups may be joined together to form a dianionic group;

any two L groups may be joined together to form a bidentate Lewis base; and

an X group may be joined to an L group to form a monoanionic bidentate group.

2. The complex of claim 1 , wherein J is selected from the following structures:

where indicates connection to the complex.

3. The complex of claim 1 , wherein the complex is further represented by Formula (II):

wherein M, L, X, m, n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 13 are as defined in claim 1 , and

E is carbon, silicon, or germanium;

R 7 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and

any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

4. The complex of claim 3 , wherein R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.

5. The complex of claim 3 , wherein E is carbon.

6. The complex of claim 3 , wherein R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl.

7. The complex of claim 1 , wherein M is Ti, Zr, or Hf.

8. The complex of claim 6 , wherein M is Ti, Zr, or Hf.

9. The complex of claim 1 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

10. The complex of claim 3 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

11. The complex of claim 1 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide.

12. The complex of claim 3 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide.

13. The complex of claim 1 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

14. The complex of claim 3 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

15. The complex of claim 1 , wherein IV is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

16. The complex of claim 3 , wherein IV is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

17. The complex of claim 1 , wherein R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

18. The complex of claim 3 , wherein R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

19. The complex of claim 1 , wherein J is dihydro-1H-indenyl and R 1 is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

20. The complex of claim 1 , wherein R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

21. The complex of claim 3 , wherein R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

22. The complex of claim 3 , wherein R 10 and R 11 are joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

23. The complex of claim 3 , wherein R 10 and R 11 are joined to form a substituted or unsubstituted saturated hydrocarbyl ring, where the ring has 6 ring atoms and where substitutions on the ring can join to form additional rings.

24. The complex of claim 1 , wherein the complex is further represented by Formula:

wherein M, L, X, m, n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 13 are as defined in claim 1 ;

R 7 through R 12 and R 14 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

25. A quinolinyldiamido transition metal complex represented by Formula:

26. A catalyst system comprising an activator and the transition metal complex of claim 1 .

27. The catalyst system of claim 26 , wherein two or more catalyst complexes are present.

28. The catalyst system of claim 26 , wherein the activator is an alumoxane.

29. The catalyst system of claim 26 , wherein the activator is a non-coordinating anion.

30. The catalyst system of claim 26 , wherein the catalyst complex and/or the activator is supported.

31. A polymerization process to produce polyolefin comprising contacting one or more olefin monomers with the catalyst system of claim 26 and obtaining olefin polymer.

32. A polymerization process to produce polyolefin comprising contacting, in solution phase, one or more olefin monomers with a catalyst system comprising the complex of claim 25 and activator, at a temperature of at least 85° C., and obtaining olefin polymer, where the olefin monomers comprise ethylene and propylene.

33. The process of claim 31 , wherein the monomers comprise ethylene.

34. The process of claim 31 , wherein the monomers comprise propylene.

35. The process of claim 31 , wherein the polymerization process is a solution process.

36. The process of claim 31 , wherein the polyolefin produced is an ethylene polymer.

37. The process of claim 34 , wherein the polyolefin produced is isotactic polypropylene.

38. A catalyst system comprising the activator and the transition metal complex of claim 3 .

39. The catalyst system of claim 26 , wherein M=Hf, Zr, or Ti.

40. The catalyst system of claim 38 , wherein M=Hf, Zr, or Ti.

41. The catalyst system of claim 26 , wherein:

R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen;

R 1 is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;

R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;

J is selected from the following structures:

where indicates connection to the complex; and

M is Ti, Zr, or Hf.

42. The catalyst system of 38 , wherein:

R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen;

R 1 is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl;

R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;

R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl;

E is carbon;

R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl; and

M is Ti, Zr, or Hf.

43. A polymerization process to produce olefin comprising contacting, in solution phase, one or more olefin monomers with a catalyst system comprising the complex of claim 25 and activator, at a temperature of at least 85° C., and obtaining olefin polymer, where the olefin monomers comprise ethylene and propylene and the olefin polymer has a melt flow rate (230° C., 2.16 kg) of less than 1.0 dg/min.

44. The polymerization process of claim 32 , wherein the activator is a non-coordinating anion.