Halogenated catalysts comprising Salan ligands

1. A catalyst compound comprising a compound represented by the formula:

where M is a Group 4, 5 or 6 transition metal;

each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;

R 1 and R 11 are C 1 -C 10 hydrocarbyl radicals;

R 4 and R 14 are C 1 -C 10 hydrocarbyl radicals or fluorine;

R 6 , R 7 , R 8 , R 9 , R 10 , R 16 , R 17 , R 18 , R 19 , and R 20 are fluorine;

each R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 is independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof; and

Y is a divalent C 1 to C 20 hydrocarbyl radical.

2. The catalyst compound of claim 1 wherein two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

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

4. The catalyst compound of claim 1 wherein each X is, independently, a halogen or a C 1 to C 7 hydrocarbyl radical.

5. The catalyst compound of claim 1 wherein each X is a benzyl radical.

6. The catalyst compound of claim 1 wherein each R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 is, independently, hydrogen, a halogen, or a C 1 to C 30 hydrocarbyl radical.

7. The catalyst compound of claim 1 wherein each R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.

8. The catalyst compound of claim 1 wherein R 4 and R 14 are methyl radicals or fluorine.

9. The catalyst compound of claim 1 wherein Y is —CH 2 CH 2 — or 1,2-cyclohexylene.

10. The catalyst compound of claim 1 wherein Y is —CH 2 CH 2 CH 2 —.

11. The catalyst compound of claim 1 wherein Y is a C 1 -C 20 divalent hydrocarbyl radical comprising a linker backbone comprising from 1 to 18 carbon atoms bridging between nitrogen atoms N 1 and N 2 .

12. The catalyst compound of claim 1 , wherein Y is a C 1 -C 20 divalent hydrocarbyl radical comprising O, S, S(O), S(O) 2 , Si(R′) 2 , P(R′), N(R′), or a combination thereof, wherein each R′ is independently a C 1 -C 18 hydrocarbyl radical.

13. The catalyst compound of claim 1 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 1 and R 11 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

14. The catalyst compound of claim 1 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.

15. The catalyst compound of claim 1 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 and R 11 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

16. The catalyst compound of claim 1 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.

17. A catalyst system comprising:

an activator and a catalyst compound represented by the formula:

where M is a Group 4, 5 or 6 transition metal;

each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;

R 1 and R 11 are C 1 -C 10 hydrocarbyl radicals;

R 4 and R 14 are C 1 -C 10 hydrocarbyl radicals or fluorine;

R 6 , R 7 , R 8 , R 9 , R 10 , R 16 , R 17 , R 18 , R 19 , and R 20 are fluorine;

each R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 is independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof; and

Y is a divalent C 1 to C 20 hydrocarbyl radical.

18. The catalyst system of claim 17 , wherein two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

19. The catalyst system of claim 17 , wherein the activator comprises alumoxane, a non-coordinating anion activator, or a combination thereof.

20. The catalyst system of claim 17 , wherein the activator comprises alumoxane and the alumoxane is present at a ratio of 1 mole aluminum or more to mole of catalyst compound.

21. The catalyst system of claim 17 , wherein the activator is represented by the formula:

(Z) d + (A d− )

wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a neutral Lewis 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.

22. The catalyst system of claim 17 wherein the activator is represented by the formula:

(Z) d + (A d− )

wherein A d− is a non-coordinating anion having the charge d−;

d is an integer from 1 to 3, and

Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more C 1 to C 40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from Groups 13-17 of the periodic table of the elements, or a combination thereof.

23. The catalyst system of claim 17 wherein the activator is selected from the group consisting of:

trimethylammonium tetrakis(perfluoronaphthyl)borate,

triethylammonium tetrakis(perfluoronaphthyl)borate,

tripropylammonium tetrakis(perfluoronaphthyl)borate,

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

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

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,

N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,

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

tropillium tetrakis(perfluoronaphthyl)borate,

triphenylcarbenium tetrakis(perfluoronaphthyl)borate,

triphenylphosphonium tetrakis(perfluoronaphthyl)borate,

triethylsilylium tetrakis(perfluoronaphthyl)borate,

benzene(diazonium)tetrakis(perfluoronaphthyl)borate,

trimethylammonium tetrakis(perfluorobiphenyl)borate,

triethylammonium tetrakis(perfluorobiphenyl)borate,

tripropylammonium tetrakis(perfluorobiphenyl)borate,

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

tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,

N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,

N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,

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

tropillium tetrakis(perfluorobiphenyl)borate,

triphenylcarbenium tetrakis(perfluorobiphenyl)borate,

triphenylphosphonium tetrakis(perfluorobiphenyl)borate,

triethylsilylium tetrakis(perfluorobiphenyl)borate,

benzene(diazonium)tetrakis(perfluorobiphenyl)borate,

[4-tert-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B],

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(tert-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

tropillium tetraphenylborate,

triphenylcarbenium tetraphenylborate,

triphenylphosphonium tetraphenylborate,

triethylsilylium tetraphenylborate,

benzene(diazonium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

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

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

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

tropillium tetrakis(pentafluorophenyl)borate,

triphenylcarbenium tetrakis(pentafluorophenyl)borate,

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

triethylsilylium tetrakis(pentafluorophenyl)borate,

benzene(diazonium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

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

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

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

tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

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

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

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

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

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

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

benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,

tetrakis(pentafluorophenyl)borate,

4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,

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

combinations thereof.

24. A process to polymerize olefins comprising:

contacting one or more olefins with a catalyst system at a temperature, a pressure, and for a period of time sufficient to produce a polyolefin, the catalyst system comprising an activator and a catalyst compound represented by the formula:

where M is a Group 4, 5 or 6 transition metal;

each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;

R 1 and R 11 are C 1 -C 10 hydrocarbyl radicals;

R 4 and R 14 are C 1 -C 10 hydrocarbyl radicals or fluorine;

R 6 , R 7 , R 8 , R 9 , R 10 , R 16 , R 17 , R 18 , R 19 , and R 20 are fluorine;

each R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 is independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof; and

Y is a divalent C 1 to C 20 hydrocarbyl radical.

25. The process of claim 24 , wherein two or more of R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 , and R 22 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

26. The process of claim 24 , wherein the temperature is from about 0° C. to about 300° C., the pressure is from about 0.35 MPa to about 10 MPa, and the period of time is from about 0.1 minutes to about 24 hours.

27. The process of claim 24 , wherein the one or more olefins comprise propylene.

28. The process of claim 24 , wherein the polyolefin comprises at least 50 mole % propylene.

29. The catalyst system of claim 17 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 1 and R 11 are methyl radicals;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

30. The catalyst system of claim 17 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.

31. The catalyst system of claim 17 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 and R 11 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

32. The catalyst system of claim 17 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.

33. The process of claim 24 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 1 and R 11 are methyl radicals;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

34. The process of claim 24 wherein:

M is Ti;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.

35. The process of claim 24 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 and R 11 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen;

R 4 and R 14 are fluorine; and

Y is —CH 2 CH 2 —.

36. The process of claim 24 wherein:

M is Zr;

X 1 and X 2 are benzyl radicals;

R 1 , R 4 , R 11 and R 14 are methyl radicals;

R 2 , R 3 , R 5 , R 12 , R 13 , R 15 , R 21 and R 22 are hydrogen; and

Y is —CH 2 CH 2 —.