Method for stereospecific cycloaddition reaction
AssigneeKing Fahd University of Petroleum and Minerals
InventorsAbdul Malik PEEDIKAKKAL, Hasan Ali AL-MOHSIN
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Abstract
Metal-organic frameworks (MOFs) may have Zn(II), Pb(II), and/or Cd(II) as a central metal ion, a 4,4′-bipyridylethylene (bpe) ligand as a first ligand; and fumaric acid (fum) and/or oxalic acid (ox) as a second ligand, wherein the 4,4′-bipyridylethylene ligands are stacked in the MOF, and wherein a distance between two consecutive 4,4′-bipyridylethylene ligands is less than 5 Å. Cycloadditions, particularly photoinduced [2+2] cycloadditions may be catalyzed by such MOFs, and/or the conversion of photoinduced [2+2] cycloadditions in inventive MOFs may be increased by mechanical force, such as by grinding.
Claims20
(canceled)
2:
- The method of claim 16, wherein the metal ion of the MOF comprises Pb(II).
3:
- The method of claim 16, wherein the metal ion of the MOF comprises a first and a second Zn(II).
4:
- The method of claim 16, wherein the MOF comprises a first, second, and third oxalic acid as the second ligand.
5:
- The method of claim 16, wherein the first ligand of the MOF is protonated.
6:
- The method of claim 16, wherein the metal ion of the MOF comprises a first, second, third, and fourth Pb(II).
7-8. (canceled)
9:
- The method of claim 16, wherein the structural unit of the MOF has a formula:
- [Pb4(ox)3(bpe)4(H2O)4]n.
10:
- The method of claim 16, wherein the structural unit of the MOF has a formula:
- [Pb4(ox)3(bpe)4(H2O)4]n.(NO3)2 (2).
11:
- The method of claim 16, wherein the structural unit of the MOF has a formula:
- [Pb(bpe)(fum)]n.
12:
- The method of claim 16, wherein the structural unit of the MOF has a formula:
- [Pb(bpe)(fum)]n.0.25(H2O) (3).
13-15. (canceled)
16:
- A method of increasing the conversion of a [2+2]cycloaddition, the method comprising:
- grinding a metal organic framework (MOF) to obtain a ground MOF;
- and
- irradiating an olefinic substrate in the presence of the ground MOF with UV light,
- wherein the MOF has repeating structural units, each structural unit comprising:
- Zn(II), Pb(II), and/or Cd(II) as a metal ion;
- a 4,4′-bipyridylethylene(bpe) ligand as a first ligand;
- and
- fumaric acid (fum) and/or oxalic acid (ox) as a second ligand,
- wherein the 4,4′-bipyridylethylene ligands are stacked in the MOF, and
- wherein a distance between two consecutive 4,4′-bipyridylethylene ligands is less than 5 Angstroms, and
- wherein the first ligand is protonated.
17:
- The method of claim 16, wherein the MOF has a structural unit of formula
- [Cd(bpe)1.5(NO3)2(H2O)]n.
18-20. (canceled)
The method of claim 16, wherein the irradiating causes the olefinic substance to undergo a [2+2] cycloaddition reaction and form a compound with a cyclobutane moiety.
The method of claim 16, wherein the olefinic substance consists of a single olefinic compound and the [2+2] cycloaddition reaction is a photodimerization of the single olefinic compound.
The method of claim 16, wherein the [2+2] cycloaddition reaction proceeds stereospecifically to form a product that is at least 75% of a single isomer.
24:
- A method of synthesizing a four-membered carbon cycle, the method comprising:
- irradiating an olefinic substrate with UV light in the presence of a metal-organic framework (MOF) to form a product having a cyclobutane moiety,
- wherein the MOF has repeating structural units, each structural unit comprising:
- Zn(II), Pb(H), and/or Cd(II) as a metal ion;
- a 4,4′-bipyridylethylene (bpe) ligand as a first ligand;
- and
- fumaric acid (fum) and/or oxalic acid (ox) as a second ligand,
- wherein the 4,4′-bipyridylethylene ligands are stacked in the MOF, and
- wherein a distance between two consecutive 4,4′-bipyridylethylene ligands is less than 5 Angstroms,
- wherein the structural unit has a formula:
- {(Hbpe)2[Zn2(ox)3]}n.
25:
- A method of synthesizing a four-membered carbon cycle, the method comprising:
- irradiating an olefinic substrate with UV light in the presence of a metal-organic framework (MOF) to form a product having a cyclobutane moiety,
- wherein the MOF has repeating structural units, each structural unit comprising:
- Zn(II), Pb(II), and/or Cd(II) as a metal ion;
- a 4,4′-bipyridylethylene (bpe) ligand as a first ligand;
- and
- fumaric acid (fum) and/or oxalic acid (ox) as a second ligand,
- wherein the 4,4′-bipyridylethylene ligands are stacked in the MOF, and
- wherein a distance between two consecutive 4,4′-bipyridylethylene ligands is less than 5 Angstroms,
- wherein the structural unit has a formula:
- {(Hbpe)2[Zn2(ox)3]}n.(H2O).2.2(DMF) (1).
Dependencies are inferred from the claim text.