Tri-and bidentate amido ligands prepared by palladium0 coupling and metallation threreof to form metal-amido catalysts

• US 20030032808A1
• Filed: 04/02/2002
• Published: 02/13/2003
• Est. Priority Date: 04/02/2001
• Status: Active Grant

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Peters, Jonas C., Brown, Steven D., Harkins, Seth B.
• Granted Patent: US 6,939,969 B2
• Time in Patent Office: Days
• US Class Current: 546/2
• CPC Class Codes: C07F 15/0066 without a metal-carbon linkage
• CPC Class Codes: C07F 15/0086 Platinum compounds
• CPC Class Codes: C07F 15/045 without a metal-carbon linkage
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C07F 9/5022 Aromatic phosphines (P-C aromatic linkage)
• CPC Class Codes: C07F 9/60 Quinoline or hydrogenated quinoline ring systems
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/7054 NNN

Abstract

This invention provides an amido ligand and its synthesis. Use of the amide ligand in a variety of metal complexes, and transition metals in particular, is also provided.

Claims

1. A tri- or bidentate amido ligand having the formula:

2. The compound of claim 1 wherein R² and R³ are taken together to form a 5- or 6-membered aryl, substituted aryl, heteroaryl, or substituted heteroarl.

3. The compound of claim 2 wherein R² and R³ are taken together to form a 6-membered heteroaryl or substituted heteroaryl.

4. The compound of claim 1 wherein R¹ is selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

5. The compound of claim 4 wherein R¹ is selected from the group consisting of hydrogen and alkyl.

6. The compound of claim 1 wherein R⁴ is selected from the group consisting of hydrogen and alkyl.

7. The compound of claim 1 wherein n is 0.

8. The compound of claim 1 wherein n is 1 and L is a C_1-12 alkylene.

9. The compound of claim 1 wherein R⁵ is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl.

10. The compound of claim 9 wherein R⁵ is selected from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl.

11. The compound of claim 10 wherein R⁵ is comprised of two fused rings.

12. The compound of claim 10 wherein R⁵ is selected from the group consisting of phenyl, naphthyl, pyridinyl, or quinolyl, which are optionally substituted with one ore more alkyl, substituted alkyl, alkoxy, alkylsulfanyl, and amino moieties.

13. The compound of claim 1 wherein X is N.

14. The compound of claim 1 wherein X is P.

15. The compound of claim 1 which has the formula:

16. A method for synthesizing compounds useful as amido ligands, comprising reacting:

(a) an amino-substituted, N-heteroaryl compound; and

(b) a halogen-substituted aromatic compound;

in the presence of a transition metal catalyst.

17. The method of claim 16 wherein the transition metal catalyst comprises a metal atom and at least one chelating ligand.

18. The method of claim 17 wherein the metal atom is selected from the group consisting of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.

19. The method of claim 18 wherein the metal atom is selected from the group consisting of nickel, palladium, and platinum.

20. The method of claim 19 wherein the metal atom is Pd⁰.

21. The method of claim 18 wherein the chelating ligand comprises at least one metal atom selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth.

22. The method of claim 21 wherein the metal atom is selected from the group consisting of nitrogen, phosphorus, and arsenic.

23. The method of claim 22 wherein the metal atom is selected from the group consisting of nitrogen and phosphorus.

24. The method of claim 21 wherein the chelating ligand comprises one metal atom, and further comprises a chelating element selected from the group consisting of oxygen and sulfur.

25. The method of claim 24 wherein the chelating ligand is an arylene or metallocene substituted with at least one of said metal atoms.

26. The method of claim 25 wherein the arylene is a C_4-20 arylene.

27. The method of claim 26 wherein the C_4-20 arylene is a binaphthyl compound.

28. The method of claim 25 wherein the metallocene is ferrocene.

29. The method of claim 25 wherein the chelating ligand is bidentate and the metal atom is phosphorous.

30. The method of claim 16 wherein the transition metal catalyst is prepared in situ.

31. The method of claim 16 wherein the amino-substituted, N-heteroaryl compound has the formula:

32. The compound of claim 31 wherein R² and R³ are taken together to form a 5- or 6-membered aryl, substituted aryl, heteroaryl, or substituted heteroarl.

33. The compound of claim 32 wherein R² and R³ are taken together to form a 6-membered heteroaryl or substituted heteroaryl.

34. The compound of claim 31 wherein R⁴ is selected from the group consisting of hydrogen and alkyl.

35. The method of claim 16 wherein the halogen substituted aromatic compound has the formula:

Z—

(L)_n—

R⁵ 

 

(III)

wherein;

Z is halo;

L is hydrocarbylene;

n is 0 or 1; and

R⁵ is selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

36. The compound of claim 35 wherein R⁵ is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl.

37. The compound of claim 36 wherein R⁵ is selected from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl.

38. The compound of claim 37 wherein R⁵ is comprised of two fused rings.

39. The compound of claim 38 wherein R⁵ is selected from the group consisting of phenyl, naphthyl, pyridinyl, or quinolyl, which are optionally substituted with one ore more alkyl, substituted alkyl, alkoxy, alkylsulfanyl, and amino moieties.

40. A complex having the formula:

LM(Q)_r

wherein;

M is a metal;

each Q is independently selected from the group consisting of hydrogen, halo, pseudo-halo, alkoxy, amido, C_1-15 hydrocarbyl, and substituted C_1-15 hydrocarbyl, or, if more than one Q moieties is present, the two or more Q moieties may be taken together to form a C_5-15 cycloalkyl;

r is 1, 2, or 3; and

L is a ligand having the formula;

wherein;

R¹ is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl and substituted heteroatom-containing hydrocarbyl;

X is selected from the group consisting of N and P;

L is hydrocarbylene;

n is 0 or 1;

R⁵ is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl; and

R², R³, and R⁴ are independently selected from the group consisting of hydrogen and hydrocarbyl, or R² and R³ may be taken together to form a 5- or 6-membered ring structure selected from the group consisting of cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroarl;

with the proviso that when R² and R³ are taken together to form a 6-membered unsubstituted aryl ring, R¹ and R⁴ are H, and n is 0, then R⁵ may not be a quinoline moiety connected at the C₈ position.

41. The complex of claim 40 wherein R² and R³ are taken together to form a 5- or 6-membered aryl, substituted aryl, heteroaryl, or substituted heteroarl.

42. The complex of claim 41 wherein R² and R³ are taken together to form a 6-membered heteroaryl or substituted heteroaryl.

43. The complex of claim 40 wherein R¹ is selected from the group consisting of hydrogen and alkyl.

44. The complex of claim 40 wherein R⁴ is selected from the group consisting of hydrogen and alkyl.

45. The complex of claim 40 wherein n is 0.

46. The complex of claim 40 wherein n is 1 and L is a C-_1-12 alkylene.

47. The compound of claim 40 wherein R⁵ is selected from the group consisting of hydrocarbyl and substituted hydrocarbyl.

48. The compound of claim 47 wherein R⁵ is selected from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl.

49. The compound of claim 48 wherein R⁵ is comprised of two fused rings.

50. The compound of claim 49 wherein R⁵ is selected from the group consisting of phenyl, naphthyl, pyridinyl, or quinolyl, which are optionally substituted with one ore more alkyl, substituted alkyl, alkoxy, alkylsulfanyl, and amino moieties.

51. The complex of claim 40 wherein X is N.

52. The complex of claim 40 wherein X is P.

53. The complex of claim 40 wherein M is selected from the group consisting of zinc;

thallium;

metals from Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the Periodic Table of the Elements;

the lanthamides; and

the actinides.

54. The complex of claim 53 wherein M is selected from the group consisting of zirconium, manganese, zinc, thallium, thorium, uranium, and metals from Group 8, Group 9, and Group 10 of the Periodic Table of the Elements.

55. The complex of claim 54 wherein M is selected from the group consisting of nickel, palladium, and platinum.

56. The complex of claim 40 wherein Q is selected from the group consisting of halo, pseudo-halo, and alkyl.