(Di)silicon bridged metallocenes that produce polyethylene with broad molecular weight distribution and high molecular weight

1. A catalyst compound represented by formula (I):

wherein:

M is a group 4 metal;

Y 1 and Y 2 are independently Si, Ge, or C, where at least one of Y 1 and Y 2 is not C;

X 1 and X 2 are independently hydrogen, halide, hydroxyl, or C 1 -C 50 substituted or unsubstituted hydrocarbyl, alkoxide, or combination thereof, or X 1 and X 2 are joined together to form a metallocycle ring, or X 1 and X 2 are joined to form a chelating ligand, or an alkylidene;

each of R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, halogen, C 1 -C 50 hydrocarbyl or C 1 -C 50 substituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, siloxyl, or one or more of R 1 and R 2 , R 2 and R 3 , and R 5 and R 6 , are joined to form a saturated cyclic ring, substituted saturated cyclic ring, a substituted unsaturated cyclic ring, or an unsubstituted unsaturated cyclic ring;

R 4 is halogen, silylcarbyl, substituted silylcarbyl, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, fluorenylidenyl, substituted fluorenylidenyl, or —NR′ 2 , —SR′, —OR, —OSiR′ 3 , —PR′ 2 , where each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or R 3 and R 4 , are joined to form a saturated cyclic ring, substituted saturated cyclic ring, a substituted unsaturated cyclic ring, or an unsubstituted unsaturated cyclic ring, or R 4 is hydrogen and R 2 and R 3 are joined to form a saturated cyclic ring, substituted saturated cyclic ring, or an unsubstituted unsaturated cyclic ring;

R 8 is halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, silylcarbyl, silyl, substituted silylcarbyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, —NR′ 2 , —SR′, —OR, —OSiR′ 3 , —PR′ 2 , where each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or phenyl.

2. The catalyst compound of claim 1 , wherein-R 8 is hydrogen, halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, silylcarbyl, silyl, substituted silylcarbyl, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, —NR′ 2 , —SR′, —OR, —OSiR′ 3 , —PR′ 2 , where each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or phenyl.

3. The catalyst compound of claim 1 , wherein X 1 and X 2 are independently halide, C 1 -C 10 hydrocarbyl, or C 1 -C 10 substituted hydrocarbyl.

4. The catalyst compound of claim 1 , wherein R 4 is halogen, C 6 -C 10 aryl, substituted C 6 -C 10 aryl, fluorenylidenyl, or substituted fluorenylidenyl.

5. The catalyst compound of claim 1 , wherein R 8 is C 1 -C 20 hydrocarbyl or substituted C 1 -C 20 hydrocarbyl.

6. The catalyst compound of claim 1 , wherein R 8 is substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.

7. The catalyst compound of claim 1 , wherein R 2 and R 3 combine to form a cyclobutyl ring, a cyclopentyl ring, or cyclohexyl ring.

8. The catalyst compound of claim 1 , wherein R 6 is hydrogen, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.

9. The catalyst compound of claim 1 , wherein M is Ti, Hf, or Zr.

10. The catalyst compound of claim 1 , wherein Y 1 and Y 2 are Si.

11. A catalyst compound represented by a formula below, where the Zr in each formula is optionally replaced by Hf:

12. A catalyst system comprising: (a) the catalyst compound of claim 1 , and (b) an activator.

13. The catalyst system of claim 12 , wherein one catalyst compound represented by formula (I) is present.

14. The catalyst system of claim 12 further comprising: (c) a bridged or unbridged metallocene catalyst compound other than the catalyst of compound (a).

15. The catalyst system of claim 12 , further comprising a support material.

16. The catalyst system of claim 12 , wherein the activator comprises one or more of:

N,N-dimethylanilinium tetra(perfluorophenyl)borate,

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,

N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,

N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

triphenylcarbenium tetrakis(perfluoronaphthyl)borate,

triphenylcarbenium tetrakis(perfluorobiphenyl)borate,

triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

triphenylcarbenium tetra(perfluorophenyl)borate,

trimethylammonium tetrakis(perfluoronaphthyl)borate,

triethylammonium tetrakis(perfluoronaphthyl)borate,

tripropylammonium tetrakis(perfluoronaphthyl)borate,

tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, and

tropillium tetrakis(perfluoronaphthyl)borate.

17. The catalyst system of claim 12 , wherein the activator comprises alkylalumoxane.

18. The catalyst system of claim 15 , wherein the support material is selected from the group consisting of Al 2 O 3 , ZrO 2 , SiO 2 , and SiO 2 /Al 2 O 3 .

19. The catalyst system of claim 18 , wherein the support material is fluorided.

20. The catalyst system of claim 15 , wherein the support material is silica.

21. A method of polymerizing olefins to produce a polyolefin comprising:

contacting at least one olefin with the catalyst system of claim 12 ; and

obtaining a polyolefin.

22. The method of claim 21 , wherein

R 4 is halogen, C 6 -C 10 aryl, or C 6 -C 10 substituted aryl;

R 6 is methyl; and

R 8 is C 3 -C 10 substituted hydrocarbyl or C 3 -C 10 unsubstituted hydrocarbyl.

23. The method of claim 21 , further comprising alkylalumoxane present at a molar ratio of aluminum to catalyst compound group 4 metal of 100:1 or more.

24. The method of claim 21 , wherein the catalyst system further comprises an activator represented by the formula:

(Z) d + (A d− )

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

25. The method of claim 21 , wherein the catalyst system further comprises an activator represented by the formula:

(Z) d + (A d− )

wherein A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3;

Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl or heteroaryl a C 1 to C 40 hydrocarbyl, or a substituted C 1 -C 40 hydrocarbyl.

26. The method of claim 21 , wherein the method occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 MPa to 10 MPa, and at a time up to 300 min.

27. The method of claim 21 , wherein the olefins comprise ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

28. The method of claim 21 , further comprising introducing the first catalyst compound represented by Formula (I) into a reactor as a slurry.

29. The method of claim 21 , wherein the polymer produced has a Mw/Mn greater than 3.5.

30. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 3.5 or more and a g′ vis of 0.98 or more.

31. The method of claim 21 , wherein the polymer produced has a Mw/Mn greater than 6.

32. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 6 or more and a g′ vis of 0.98 or more and total unsaturation/1000 C of 0.15 or less.

33. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 3.5 or more, a g′ vis of 0.98 or more, and a zero or positive slope that transitions to a negative slope in the GPC-4D plot of comonomer incorporation vs molecular weight (log M).

34. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 2 or more, a g′ vis of 0.98 or more, and a zero or positive slope that transitions to a negative slope in the GPC-4D plot of comonomer incorporation vs molecular weight (log M)).

35. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 3 or more, a g′ vis of 0.98 or more, and a zero or positive slope that transitions to a negative slope in the GPC-4D plot of comonomer incorporation vs molecular weight (log M).

36. The method of claim 21 , wherein the polymer produced has a Mw/Mn of 2 or more, preferably 2.5 or more, a g′ vis of 0.98 or more, preferably 0.99 or more, more preferably 1.0 or more, and a zero or positive slope in the GPC-4D plot of comonomer incorporation vs molecular weight (log M)).

37. The method of claim 21 , wherein the method occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 MPa to 10 Mpa, and at a time up to 300 min and the polyolefin produced has a total unsaturation/1000 C of 0.8 or less, preferably 0.7 or less.

38. The method of claim 21 , wherein the method occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 Mpa to 10 Mpa, and at a time up to 300 min and the polyolefin produced has a total unsaturation/1000 C of 1.0 or less.

39. The method of claim 21 , wherein the method occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 Mpa to 10 Mpa, and at a time up to 300 min and the polyolefin produced has an Mw/Mn of 6 or more and total unsaturation/1000 C of 0.15 or less.

40. The compound of claim 1 , wherein R 3 and R 4 are joined to form a saturated cyclic ring, substituted saturated cyclic ring, a substituted unsaturated cyclic ring, or an unsubstituted unsaturated cyclic ring.

41. The catalyst compound of claim 1 , wherein R 7 , R 9 and R 10 are H.

42. A catalyst system comprising the catalyst compound of claim 2 and an activator.

43. A catalyst system comprising the catalyst compound of claim 11 and an activator.

44. A catalyst compound represented by a formula below, where the Zr in each formula is optionally replaced by Hf:

45. The catalyst compound of claim 44 , wherein the Zr in each formula is not optionally replaced by Hf.