Phospho-amino pincer-type ligands and catalytic metal complexes thereof

• US 8,598,351 B2
• Filed: 06/20/2012
• Issued: 12/03/2013
• Est. Priority Date: 06/20/2011
• Status: Active Grant

• Current Assignee: King Abdullah University of Science and Technology
• Original Assignee: King Abdullah University of Science and Technology
• Inventors: Huang, Kuo-Wei, He, Lipeng, Gong, Dirong, Jia, Weiguo, Yao, Liangfeng, Chen, Tao
• Primary Examiner(s): Andres, Janet L
• Assistant Examiner(s): Rozof, Timothy R
• Application Number:
  US13/528,481
• Publication Number:
  US 20120323007A1
• Time in Patent Office: 531 Days
• Field of Search: None
• US Class Current: 546/2
• CPC Class Codes: C07C 29/143 of ketones
• CPC Class Codes: C07C 31/125 containing five to twenty-two carbon atoms
• CPC Class Codes: C07C 33/22 Benzylalcohol; phenethyl alcohol
• CPC Class Codes: C07C 35/08 containing a six-membered rings
• CPC Class Codes: C07C 67/40 by oxidation of primary alcohols
• CPC Class Codes: C07C 69/24 esterified with monohydroxylic compounds
• CPC Class Codes: C07C 69/78 Benzoic acid esters
• CPC Class Codes: C07F 15/0046 Ruthenium compounds
• CPC Class Codes: C07F 15/0066 without a metal-carbon linkage
• CPC Class Codes: C07F 15/045 without a metal-carbon linkage
• CPC Class Codes: C07F 15/065 without a metal-carbon linkage
• CPC Class Codes: C07F 9/58 Pyridine rings
• CPC Class Codes: C07F 9/65583 each of the hetero rings containing nitrogen as ring hetero atom

Abstract

The present invention provides phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes.

Claims

1. A compound of the formula:

2. The compound of claim 1, wherein R₁ and R₂ are each tert-butyl.

3. The compound of claim 1, wherein R₃ is selected from the group consisting of formulas:

4. The compound of claim 1, wherein R₃ is formula (a).

5. The compound of claim 4, wherein R_a and R_b are hydrogen.

6. The compound of claim 4, wherein R₄ and R₅ are each alkyl_(C≦

8).

7. The compound of claim 6, further defined as:

8. The compound of claim 1, wherein R₃ is formula (b).

9. The compound of claim 8, wherein R₆ and R₇ are each alkyl_(C≦

8).

10. The compound of claim 9, wherein R₆ and R₇ are each methyl.

11. The compound of claim 8, wherein R₈ and R₉ are each hydrogen.

12. The compound of claim 11, further defined as:

13. The compound of claim 1, wherein R₃ is formula (c).

14. The compound of claim 13, further defined as:

15. The compound of claim 1, wherein R₃ is formula (d).

16. The compound of claim 15, further defined as:

17. The compound of claim 15 wherein R₁₁ and R₁₂ are each alkyl_(C≦

8).

18. The compound of claim 17, further defined as:

19. The compound of claim 1, further defined as:

20. A complex comprising a ligand and a metal or metal ion, wherein the ligand is a compound according to claim 1, or a deprotonated version thereof, and the ligand is chemically bound to the metal or metal ion in a 1:

1 ratio.

21. The complex of claim 20, wherein the metal or metal ion is a group 8 metal or metal ion.

22. The complex of claim 21, wherein the metal or metal ion is based on ruthenium.

23. The complex according to claim 20, wherein the complex further comprises a second ligand, wherein the second ligand is chloride.

24. The complex according to claim 20, wherein the complex further comprises a third ligand, wherein the third ligand is carbon monoxide.

25. The complex of claim 24, further defined by the formula:

26. The complex of claim 20, wherein the metal or metal ion is a group 9 metal or metal ion.

27. The complex of claim 26, wherein the metal or metal ion is based on cobalt.

28. A method for the preparation of an ester of Formula III comprising reacting two or more alcohols of Formula II:

29. A method for the preparation of an imine of Formula V comprising reacting two or more alcohols of Formula II: