Quinolinyldiamido transition metal complexes, production and use thereof

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

wherein:

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

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 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,

E is carbon, silicon, or germanium;

R 7 through R 9 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,

R 12 is selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen,

R 10 and R 11 are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls,

where R 10 and R 11 are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

2. A quinolinyldiamido transition metal complex represented by Formula (II):

wherein:

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

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,

E is carbon, silicon, or germanium;

R 7 and R 8 are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls,

R 9 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and

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,

where R 7 and R 8 are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

3. The complex of claim 1 , wherein E is carbon.

4. The complex of claim 2 , wherein E is carbon.

5. The complex of claim 2 , wherein M is Ti, Zr, of Hf.

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

7. 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.

8. The complex of claim 2 , 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.

9. 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.

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

11. 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.

12. The complex of claim 2 , 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.

13. The complex of claim 1 , wherein 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.

14. The complex of claim 2 , wherein R 1 is 2,6-diisopropylphenyl, 2,4,6-triisoproplphenyl, 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.

15. 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-fluorphenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

16. The complex of claim 2 , 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.

17. 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.

18. The complex of claim 2 , 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.

19. The complex of claim 2 , 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.

20. The complex of claim 2 , 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.

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

22. The catalyst system of claim 21 , wherein the activator is an alumoxane.

23. The catalyst system of claim 21 , wherein the activator is a non-coordinating anion.

24. The catalyst system of claim 21 , wherein the catalyst complex and/or the activator is supported.

25. A polymerization process to produce polyolefin comprising contacting one or more olefin monomers with the catalyst system of claim 21 and obtaining olefin polymer.

26. 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 1 and activator, at a temperature of at least 85° C., and obtaining olefin polymer, where the olefin monomers comprise ethylene and propylene.

27. The process of claim 25 , wherein the monomers comprise ethylene.

28. The process of claim 25 , wherein the monomers comprise propylene.

29. The process of claim 25 , wherein the polymerization process is a solution process.

30. The process of claim 25 , wherein the polyolefin produced is an ethylene polymer.

31. The process of claim 28 , wherein the polyolefin produces is isotactic polypropylene.

32. A catalyst system comprising the activator and the transition metal complex of claim 2 .

33. The catalyst system of claim 21 , wherein M=Hf, Zr, or Ti.

34. The catalyst system of claim 32 , wherein M=Hf, Zr, or Ti.

35. 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 2 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.

36. The polymerization process of claim 26 , wherein the activator is a non-coordinating anion.

37. The complex of claim 1 , wherein R 10 and R 11 are joined to form a five membered ring with the joined R 10 R 11 group being —CH 2 CH 2 —.

38. The complex of claim 1 , wherein R 10 and R 11 are joined to form a six membered ring with the joined R 10 R 11 group being —CH 2 CH 2 CH 2 —.

39. The complex of claim 2 , wherein R 7 and R 8 are joined to form a six-membered aromatic ring with the joined R 7 R 8 group being —CH═CHCH═CH—.

40. The complex of claim 2 , wherein M is Hf; R 2 to R 6 are H; X is NMe 2 or Me; n is 2; y is 0 and L is not present; R 1 is 2,6-diisopropylphenyl; R 13 is 2-methylphenyl, 2,6-dimethylphenyl, or phenyl; R 12 is H; R 11 forms a ring with R 10 ; R 9 is H; and R 7 and R 8 are joined together to form a six-membered aromatic ring.

41. A process to produce a quinolinyldiamide ligand comprising contacting compound (III) with compound (IV) to produce quinolinyldiaimine (V) in a coupling reaction, wherein compound (III), compound (IV) and the quinolinyldiaimine (V) are represented by the formula:

wherein;

W* and Y* are each independently selected from boronic acid ester, halide, alkali metal, alkaline earth metal halide, zinc halide, zincate, and triflate;

E is carbon, silicon, or germanium;

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;

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;

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.

42. The process of claim 41 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.

43. A process to produce a transition metal quinolinyldiamide complex by reaction of quinolinyldiamine (V) with a metal reactant containing anionic basic leaving groups, wherein the quinolinyldiamine (V) is represented by the formula:

wherein;

E is carbon, silicon, or germanium;

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;

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;

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.

44. A process to produce a dialkylated quinolinyldiamide complex by reaction of quinolinyldiamido complex (VI) with an organolithium, Grignard, or organoaluminum reagent, wherein quinolinyldiamido complex (VI) is represented by the formula:

wherein,

X* is a halide, alkoxide, or dialkylamido;

E is carbon, silicon, or germanium;

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;

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;

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.