Zirconium- and hafnium-based metal-organic frameworks as epoxide ring-opening catalysts
Metal-organic frameworks (MOFs) and method of using the MOFs to catalyze reactions involving epoxide ring-opening mechanisms are provided. The structure of the MOFs can be represented by the formula: M 6 (μ 3 -ligand) 8 (OH x ) 8 (TBAPy) 2 , where M is Zr or Hf, the ligands are selected from hydroxo-, oxo- and aquo-ligands, and x is independently selected from 1 or 2.
1. A method of catalyzing a reaction using a metal-organic framework comprising inorganic nodes that comprise an octahedral M 6 cluster capped by eight μ 3 -ligands and having twelve octahedral edges, wherein M is Zr or Hf and the μ 3 -ligands are hydroxo ligands, oxo ligands or aquo ligands; and organic linkers connecting the inorganic nodes, the organic linkers comprising 1,3,6,8-tetrakis(p-benzoic acid)pyrene units; wherein eight of the twelve octahedral edges of the inorganic nodes are connected to the 1,3,6,8-tetrakis(p-benzoic acid)pyrene units, the method comprising:
combining an epoxide ring-containing molecule with a reactant in the presence of a catalytic amount of the metal-organic framework in a solution, wherein the metal-organic framework catalyzes a nucleophilic epoxide ring opening of the epoxide ring-containing molecule to provide an activated epoxide and the activated epoxide reacts with the reactant to form a product molecule.
2. The method of claim 1 , wherein the epoxide ring-containing molecule comprises an aryl-substituted epoxide.
3. The method of claim 2 , wherein the epoxide ring-containing molecule is a styrene oxide.
4. The method of claim 3 , wherein the styrene oxide is a methylstyrene oxide.
5. The method of claim 1 , wherein the epoxide ring-containing molecule comprises an alkyl-substituted epoxide.
6. The method of claim 5 , wherein the epoxide ring-containing molecule is ethylene oxide, propylene oxide, or a derivative thereof.
7. The method of claim 1 , wherein the reactant is carbon dioxide and the product molecule is a cyclic carbonate.
8. The method of claim 7 , wherein the epoxide ring-containing molecule comprises an aryl-substituted epoxide.
9. The method of claim 8 , wherein the epoxide ring-containing molecule is a styrene oxide.
10. The method of claim 9 , wherein the styrene oxide is a methylstyrene oxide.
11. The method of claim 7 , wherein the epoxide ring-containing molecule comprises an alkyl-substituted epoxide.
12. The method of claim 11 , wherein the epoxide ring-containing molecule is ethylene oxide, propylene oxide, or a derivative thereof.
13. The method of claim 1 , wherein the reactant is an azide and the product molecule is a β-azidohydrin.
14. The method of claim 13 , wherein the epoxide ring-containing molecule comprises an aryl-substituted epoxide.
15. The method of claim 14 , wherein the epoxide ring-containing molecule is a styrene oxide.
16. The method of claim 15 , wherein the styrene oxide is a methylstyrene oxide.
17. The method of claim 13 , wherein the epoxide ring-containing molecule comprises an alkyl-substituted epoxide.
18. The method of claim 17 , wherein the epoxide ring-containing molecule is ethylene oxide, propylene oxide, or a derivative thereof.
19. The method of claim 1 , wherein the reactant is an alcohol and the product molecule is a β-alkoxy alcohol.
20. The method of claim 19 , wherein the epoxide ring-containing molecule comprises an aryl-substituted epoxide.
21. The method of claim 20 , wherein the epoxide ring-containing molecule is a styrene oxide.
22. The method of claim 21 , wherein the styrene oxide is a methylstyrene oxide.
23. The method of claim 19 , wherein the epoxide ring-containing molecule comprises an alkyl-substituted epoxide.
24. The method of claim 23 , wherein the epoxide ring-containing molecule is ethylene oxide, propylene oxide, or a derivative thereof.
25. The method of claim 1 , wherein the reactant is a hydride and the product molecule is a primary alcohol.
26. The method of claim 25 , wherein the hydride is cyanoborohydride.
27. The method of claim 25 , wherein the epoxide ring-containing molecule comprises an aryl-substituted epoxide.
28. The method of claim 27 , wherein the epoxide ring-containing molecule is a styrene oxide.
29. The method of claim 28 , wherein the styrene oxide is a methylstyrene oxide.
30. The method of claim 25 , wherein the epoxide ring-containing molecule comprises an alkyl-substituted epoxide.
31. The method of claim 30 , wherein the epoxide ring-containing molecule is ethylene oxide, propylene oxide, or a derivative thereof.