Pyridyldiamido transition metal complexes, production and use thereof

1. A pyridyldiamido transition metal complex represented by the formula: (I) or (II):

wherein:

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

R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;

R 11 is selected from the group consisting of substituted 5 or 6 membered aromatic rings;

R 10 is -E*(R 12 )(R 13 )—;

E and E* are, independently, carbon, silicon, or germanium;

each R 12 and R 13 is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;

each R 12 * and R 13 * is independently selected from the group consisting of hydrogen, C1 to C5 hydrocarbyls, and substituted C1 to C5 hydrocarbyls;

R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) 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 6 , R 7 , R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;

L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1, 2, 3, or 4;

L′ is neutral Lewis base;

w is 0, 1, 2, 3, or 4;

Z is —(R 14 *) p Q-J(R 15 *) q — where Q or J is bonded to R 10 ;

J is C or Si;

Q is C, N, or Si;

R 14 * and R 15 * are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 * and R 15 * groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;

p is 1 or 2; and

q is 1 or 2.

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

3. The complex of claim 1 , wherein R 10 is represented by the formula:

where R 12 ″ is hydrogen, alkyl, aryl, or halogen; and R 13 ″ is hydrogen, alkyl, aryl, or halogen.

4. The complex of claim 1 , wherein R 6 , R 7 , R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.

5. The complex of claim 1 , wherein R 1 , R 3 , R 4 , and R 5 each contain no more than 30 carbon atoms.

6. The complex of claim 4 , wherein R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 15 each contain no more than 30 carbon atoms.

7. The complex of claim 1 , wherein E and E* are carbon and R 1 is selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF 3 , NO 2 , alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyls groups with from one to ten carbons.

8. The complex of claim 1 , wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl; and each L′ is independently selected from the group consisting of ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines.

9. The complex of claim 1 , wherein both R 12 and R 13 are a C 1 to C 100 alkyl group.

10. The complex of claim 1 , wherein the complex is represented by formula (I).

11. The complex of claim 1 , wherein the complex is represented by formula (II).

12. The complex of claim 1 , wherein R 12 * and R 13 * are the same.

13. The complex of claim 1 , wherein the complex is represented by formula (I) and R 12 * is H, R 13 * is a group containing from 1 to 5 carbons, M is a Group 4 metal, E is carbon and R 10 is CH 2 .

14. The complex of claim 1 , wherein the complex is represented by formula (II) and R 12 * is a group containing from 1 to 5 carbons, M is a Group 4 metal, E is carbon and R 10 is CH 2 .

15. The complex of claim 1 , wherein M is a Group 4 metal, E* is carbon and R 10 is CH 2 .

16. The complex of claim 1 , wherein R 11 is selected from the group consisting of substituted 6 membered aromatic rings.

17. The complex of claim 1 , wherein R 11 is selected from the group consisting of substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring and where the substitution is a hydrocarbyl group, a heteroatom, or a heteroatom containing group.

18. The complex of claim 1 , wherein R 11 is a substituted aryl group.

19. The complex of claim 1 , wherein R 11 is a 2,6 or 2,4,6 substituted aryl group.

20. The complex of claim 1 , wherein R 11 is a 2,6 or 2,4,6 substituted aryl, where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, or triethylsilyl.

21. The complex of claim 1 , wherein R 11 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisobutylphenyl, 2,5-dimethylphenyl, 2,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2,6-diisopropylphenyl, or 2,4,6-triisopropylphenyl.

22. A process for preparing the pyridyldiamido complex of claim 2 comprising reaction of a pyridyldiamine with a group 4 transition metal complex of the general formula MY 2 L 2 L′ W , where M is Ti, Zr, or Hf, Y is a deprotonated amine or hydrocarbanion group; L is an anionic leaving group, where the L and Y groups may be the same or different and any two L and/or Y groups may be linked to form a dianionic group; L′ is neutral Lewis base; and w is 0, 1, 2, 3, or 4.

23. A catalyst system comprising an activator and the complex of claim 1 .

24. The catalyst system of claim 23 , wherein the activator is an alumoxane.

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

26. A polymerization process comprising a) contacting one or more alkene monomers with a catalyst system comprising: i) an activator and ii) the pyridyldiamido transition metal complex of claim 1 .

27. The process of claim 26 , wherein the activator is an alumoxane.

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

29. The process of claim 26 , wherein the monomer comprises ethylene.

30. The process of claim 26 , wherein the monomer comprises propylene.

31. The process of claim 26 , wherein the pyridyldiamido transition metal complex is supported.

32. The process of claim 26 , wherein R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.

33. The process of claim 26 , wherein R 11 is selected from the group consisting of substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring and where the substitution is a hydrocarbyl group, a heteroatom, or a heteroatom containing group.

34. The process of claim 26 , wherein R 11 is a 6 membered ring.

35. The process of claim 26 , wherein R 11 is a 2,6 or 2,4,6 substituted aryl, where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, or triethylsilyl.