Phosphinate ruthenium complexes

1. A method of catalyzing an olefin metathesis reaction, comprising contacting a ruthenium complex of Formula I with an olefin compound having two or more olefin groups;

wherein:

L is a neutral ligand;

R 1 is C 1-12 alkyl, C 3-10 cycloalkyl, C 6-14 aryl, heteroaryl, heterocyclyl, or —NR 3b R 3c ;

R 2 is H, C 1-12 alkyl, C 3-10 cycloalkyl, or C 6-14 aryl;

R 3 is halo, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, heteroaryl, heterocyclyl, —C(O)R 3a , —C(O)OR 3a , —C(O)NR 3b R 3c , —OR 3a , —NR 3b R 3c , —NR 3a C(O)R 3b , —NR 3a C(O)OR 3b , —NR 3a S(O) 2 R 3b , —PR 3a R 3b , —P(OR 3a )R 3b , —P(OR 3a )(OR 3b ), —P(O)R 3a R 3b , —P(O)(OR 3a )R 3b , —P(O)(OR 3a )(OR 3b ), —S(O) 2 R 3a , or —SO 2 NR 3b R 3c ,

R 4 is C 1-12 alkyl, C 3-10 cycloalkyl, C 7-15 aralkyl, or —C(R 4a R 4b )C(O)NR 4c R 4d ;

R 5 is hydrogen, C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 3-10 cycloalkyl, or C 6-14 aryl;

each R 3a and R 3d is independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, heteroaryl, or heterocyclyl;

each R 3b and R 3c is independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, heteroaryl, or heterocyclyl; or R 3b and R 3c together with the N atom form a heteroaryl or heterocyclyl;

R 4a and R 4b are each independently hydrogen, C 1-6 alkyl, C 3-8 cycloalkyl, C 6-14 aryl, or C 7-15 aralkyl; and

R 4c and R 4d are each independently hydrogen, C 1-6 alkyl, C 3-8 cycloalkyl, C 6-14 aryl, or C 7-15 aralkyl; or R 4c and R 4d together with the N atom form heterocyclyl;

X 1 and X 2 are each independently an anionic ligand;

Y is a bond or —NR b —;

Z is O or S; and

n is an integer of 0, 1, 2, or 3;

wherein each alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, heterocyclyl, and heteroaryl is optionally substituted with one or more groups, each independently selected from (a) cyano, halo, or nitro; (b) C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, C 7-15 aralkyl, heteroaryl, or heterocyclyl, each optionally substituted with one or more substituents Q; or (c) —C(O)R a , —C(O)OR a , —C(O)NR b R c , —C(NR a )NR b R c , —OR a , —OC(O)R a , —OC(O)OR a , —OC(O)NR b R c , —OC(═NR a )NR b R c , —OS(O)R a , —OS(O) 2 R a , —OS(O)NR b R c , —OS(O) 2 NR b R c , —NR b R c , —NR a C(O)R d , —NR a C(O)OR d , —NR a C(O)NR b R c , —NR a C(═NR d )NR b R c , —NR a S(O)R d , —NR a S(O) 2 R d , —NR a S(O)NR b R c , —NR a S(O) 2 NR b R c , —PR a R d , —P(OR a )R d , —P(OR a )(OR d ), —P(O)R a R d , —P(O)(OR a )R d , —P(O)(OR a )(OR d ), —SR a , —S(O)R a , —S(O) 2 R a , or —SO 2 NR b R c ; wherein each R a , R b , R c , and R d is independently hydrogen; C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, C 7-15 aralkyl, heteroaryl, or heterocyclyl, each optionally substituted with one or more substituents Q; or R b and R c together with the N atom to which they are attached form heterocyclyl, optionally substituted with one or more substituents Q;

wherein each Q is independently selected from the group consisting of (i) cyano, halo, or nitro; (ii) C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, C 7-15 aralkyl, heteroaryl, or heterocyclyl; or (iii) —C(O)R e , —C(O)OR e , —C(O)NR f R g , —C(NR e )NR f R g , —OR e , —OC(O)R e , —OC(O)OR e , —OC(O)NR f R g , —OC(═NR e )NR f R g , —OS(O)R e , —OS(O) 2 R e , —OS(O)NR f R g , —OS(O) 2 NR f R g , —NR f R g , —NR e C(O)R h , —NR e C(O)OR h , —NR e C(O)NR f R g , —NR e C(═NR h )NR f R g , —NR e S(O)R h , —NR e S(O) 2 R h , —NR e S(O)NR f R g , —NR e S(O) 2 NR f R g , —PR e R h , —P(OR e )R h , —P(OR e )(OR h ), —P(O)R e R h , —P(O)(OR e )R h , —P(O)(OR e )(OR h ), —SR e , —S(O)R e , —S(O) 2 R e , or —S(O) 2 NR f R g ; wherein each R e , R f , R g , and R h is independently hydrogen; C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, C 7-15 aralkyl, heteroaryl, or heterocyclyl; or R f and R g together with the N atom to which they are attached form heterocyclyl.

2. The method of claim 1 , wherein the ruthenium complex of claim 1 has Formula Ia:

3. The method of claim 1 , wherein the ruthenium complex of claim 1 has Formula Ib:

4. The method of claim 1 , wherein the ruthenium complex of claim 1 has Formula Ic:

5. The method of claim 1 , wherein L is a heterocyclic carbene or phosphine, wherein the heterocyclic carbene is optionally substituted with one or more substituents.

6. The method of claim 5 , wherein the heterocyclic carbene is selected from the group consisting of:

wherein:

each R 11 and R 12 is independently C 1-6 alkyl or C 6-14 aryl; and

each R 13 , R 14 , R 15 , and R 16 is independently hydrogen, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 6-14 aryl, heteroaryl, or heterocyclyl;

wherein each alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heterocyclyl, and heteroaryl is optionally substituted with one or more substituents.

7. The method of claim 6 , wherein R 13 or R 15 is hydrogen or methyl.

8. The method of claim 6 , wherein R 14 or R 16 is hydrogen or methyl.

9. The method of claim 6 , wherein R 11 is C 6-14 aryl.

10. The method of claim 6 , wherein R 11 is C 6-14 aryl, substituted with one or more C 1-6 alkyl.

11. The method of claim 10 , wherein R 11 is 2-methylphenyl, 2,4,6-trimethylphenyl, or 2,6-di(isopropyl)phenyl.

12. The method of claim 6 , wherein R 12 is C 6-14 aryl.

13. The method of claim 6 , wherein R 12 is C 6-14 aryl, substituted with one or more C 1-6 alkyl.

14. The method of claim 6 , wherein R 12 is 2-methylphenyl, 2,4,6-trimethylphenyl, or 2,6-di(isopropyl)phenyl.

15. The method of claim 6 , wherein the heterocyclic carbene is selected from the group consisting of:

16. The method of claim 5 , wherein the phosphine is PR 17 R 18 R 19 , wherein R 17 , R 18 , and R 19 are each independently C 1-12 alkyl or C 6-14 aryl, each optionally substituted with one or more substituents.

17. The method of claim 16 , wherein R 17 is phenyl or cyclohexyl.

18. The method of claim 16 , wherein R 18 is phenyl or cyclohexyl.

19. The method of claim 16 , wherein R 19 is phenyl or cyclohexyl.

20. The method of claim 16 , wherein the phosphine is triphenylphosphine or tricyclohexylphosphine.

21. The method of claim 1 , wherein X 1 is halide, —C(O)R x , or —OC(O)R x , wherein R x is alkyl, optionally substituted with one or more halides.

22. The method of claim 21 , wherein X 1 is chloride.

23. The method of claim 1 , wherein X 2 is halide, —C(O)R x , or —OC(O)R x , wherein R x is alkyl, optionally substituted with one or more halides.

24. The method of claim 1 , wherein X 2 is chloride.

25. The method of claim 1 , wherein R 1 is C 1-5 alkyl, C 5-6 cycloalkyl, C 6-14 aryl, heteroaryl, heterocyclyl, or —NR 3b R 3c .

26. The method of claim 1 , wherein R 1 is trifluoromethyl, phenyl, cyanophenyl, fluorophenyl, difluorophenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, trifluoromethylsulfonylphenyl, trifluoroacetylphenyl, nitrophenyl, dinitrophenyl, trifluoroacetamidophenyl, methoxyphenyl, pentofluorophenyl, pyridyl, trifluoromethyl-thiazolyl, trifluoromethyl-pyrazolyl, or dimethylamino.

27. The method of claim 1 , wherein R 1 is phenyl, 4-cyanophenyl, 4-fluorophenyl, 3,5-difluorophenyl, 4-trifluoromethylphenyl), 3,5-bis(trifluoromethyl)phenyl, 4-trifluoromethylsulfonylphenyl, 4-trifluoroacetylphenyl, 4-nitrophenyl, 3,5-dinitrophenyl, 4-trifluoroacetamidophenyl, 4-methoxyphenyl, pentofluorophenyl, pyridyl, 4-trifluoromethylthiazolyl, or 3-trifluoromethyl-pyrazolyl, or dimethylamino.

28. The method of claim 1 , wherein R 1 is phenyl, 4-fluorophenyl, 3,5-difluorophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, or dimethylamino.

29. The method of claim 1 , wherein R 2 is C 1-5 alkyl or C 5-6 cycloalkyl.

30. The method of claim 1 , wherein R 2 is ethyl.

31. The method of claim 1 , wherein R 3 is halo, cyano, nitro, —C(O)OR 3a , —NR 3a S(O) 2 R 3b , —P(O)(OR 3a )R 3b , or —SO 2 NR 3b R 3c .

32. The method of claim 1 , wherein R 4 is C 1-5 alkyl or C 5-6 cycloalkyl.

33. The method of claim 1 , wherein R 4 is isopropyl.

34. The method of claim 1 , wherein R 5 is hydrogen, C 1-5 alkyl, or C 5-6 cycloalkyl.

35. The method of claim 1 , wherein R 5 is hydrogen.

36. The method of claim 1 , wherein Z is O.

37. The method of claim 1 , wherein n is 0.

38. The method of claim 1 , wherein the complex is selected from the group consisting of:

wherein:

Cmpd No.

Y

R 1

R 11

R 12

AP

A bond

Mes

Mes

AQ

A bond

Mes

Mes

AR

A bond

Mes

Mes

AT

A bond

Mes

Mes

C5

A bond

—N(CH 3 ) 2

Mes

Mes

D4

A bond

Mes

Mes

E6

—NH—

Mes

Mes

G2

A bond

2-MePh

2-MePh

39. The method of claim 1 , wherein the olefin compound has one terminal olefin group.

40. The method of claim 1 , wherein the olefin compound has two terminal olefin groups.

41. The method of claim 1 , wherein the molar ratio between the ruthenium complex and the olefin compound is no greater than 0.5.

42. The method of claim 1 , wherein the molar ratio between the ruthenium complex and the olefin compound is no greater than 0.05.