NOVEL IMINES WITH TUNABLE NUCLEOPHILICITY AND STERIC PROPERTIES THROUGH METAL COORDINATION: APPLICATIONS AS LIGANDS AND METALLOORGANOCATALYSTS

• US 20170246621A1
• Filed: 09/09/2015
• Published: 08/31/2017
• Est. Priority Date: 09/11/2014
• 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, ZHAO, Qianyi
• Granted Patent: US 10,399,072 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 2231/323 Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• CPC Class Codes: B01J 2231/341 1,2-additions, e.g. aldol or Knoevenagel condensations
• CPC Class Codes: B01J 2231/342 Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
• CPC Class Codes: B01J 2231/625 of CO2
• CPC Class Codes: B01J 2231/763 of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
• CPC Class Codes: B01J 2531/0244 Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/847 Nickel
• CPC Class Codes: B01J 31/0201 Oxygen-containing compounds
• CPC Class Codes: B01J 31/0212 Alkoxylates
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0274 containing silicon ligands in coordination complexes B01J31/1608
• CPC Class Codes: B01J 31/12 containing organo-metallic compounds or metal hydrides
• CPC Class Codes: B01J 31/189 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C07C 231/10 from compounds not provided for in groups C07C231/02 - C07C231/08
• CPC Class Codes: C07C 233/65 having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• CPC Class Codes: C07C 29/09 by hydrolysis
• CPC Class Codes: C07C 29/14 of a —CHO group
• CPC Class Codes: C07C 29/15 : by reduction of oxides of carbon exclusively
• CPC Class Codes: C07C 31/04 : Methanol
• CPC Class Codes: C07C 33/22 : Benzylalcohol; phenethyl alcohol
• CPC Class Codes: C07C 33/46 : containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07D 317/36 : Alkylene carbonates; Substituted alkylene carbonates
• CPC Class Codes: C07F 15/04 : Nickel compounds
• CPC Class Codes: C07F 15/045 : without a metal-carbon linkage
• CPC Class Codes: C07F 9/58 : Pyridine rings
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine.

Claims

1. A complex comprising a ligand and a metal or metal ion, M, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, M,

2. The composition of claim 1, wherein R₁, R₂, R₃, and R₄ are each a alkyl_(C2-10), each Z is CH, T is N or NR₇ and R₅ is a hydrogen atom.

3. The composition of claim 2, wherein R₁, R₂, R₃, and R₄ are each a C₄ alkyl and T is NR₇.

4. The composition of claim 3, wherein R₇ is a methyl group or a hydrogen.

5. The composition of claim 1, wherein X is a hydride.

6. The compound of any of claim 1, wherein X is a halide.

7. A compound comprising formula (II):

8. The compound of claim 7, wherein R₁, R₂, R₃, and R₄ are each a alkyl_(C2-10), each Z is CH and R₅ is a hydrogen atom.

9. The compound of claim 8, wherein R₁, R₂, R₃, and R₄ are each a C₄ alkyl.

10. The compound of claim 9, wherein R₇ is a methyl group or a hydrogen.

11. The compound of claim 7, wherein X is a hydride.

12. The compound of claim 7, wherein X is a halide.

13. A composition comprising formula (III):

14. The composition of claim 13, wherein R₁, R₂, R₃, and R₄ are each a alkyl_(C2-10), each Z is CH and R₅ is a hydrogen atom.

15. The composition of claim 14, wherein R₁, R₂, R₃, and R₄ are each a C₄ alkyl.

16. The composition of claim 14, wherein R₇ is a methyl group or a hydrogen.

17. The composition of claim 13, wherein X is a hydride.

18. The composition of claim 13, wherein X is a halide.

19. The composition of claim 13, wherein the base is an organic base.

20. The composition of claim 19, wherein the organic base is an amine or an alkoxide.

21. The composition of claim 20, wherein the amine is an alkylamine comprising NR₂₀R₂₁R₂₃, wherein R₂₀, R₂₁ and R₂₃ are each independently a hydrogen atom, alkyl_(C≦

12), aryl<sub>(C≦

12)</sub>, aralkyl<sub>(C≦

12)</sub> or a substituted version of any of these groups, wherein one or more of R₂₀, R₂₁ and R₂₂ can form a ring or an aromatic amine

22. The composition of claim 21, wherein the aromatic amine is pyridine.

23-30. -30. (canceled)