Bridged phthalocyanine- and napththalocyanine-metal complex catalysts and methods of using and purifying the same

Patent metadata

Field	Value
Publication number	US-10065980-B2
Application number	US-201615217350-A
Country	US
Kind code	B2
Filing date	Jul 22, 2016
Priority date	Jul 24, 2015
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

Various embodiments disclosed relate to bridged phthalocyanine- and napththalocyanine-metal complex catalysts and methods of using and purifying the same. In various embodiments, the present invention provides a method of purifying a catalyst. The method includes contacting a catalyst composition with acid, the catalyst composition including a catalyst, to provide an acidified catalyst composition with the catalyst dissolved therein. The method includes precipitating the catalyst, and removing the precipitated catalyst from solution, to provide a purified catalyst.

First claim

What is claimed is:

1. A method of purifying a catalyst, the method comprising:
contacting a catalyst composition with acid, the catalyst composition comprising a catalyst, to provide an acidified catalyst composition with the catalyst dissolved therein, the catalyst having the structure:

wherein
M is a metal,
axial ligand L is a solvent molecule,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

 and
at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, and a hydrophilic group;

precipitating the catalyst; and
removing the precipitated catalyst from solution, to provide a purified catalyst.

2. The method of claim 1 , wherein the precipitating comprises at least partially neutralizing the acidified composition.

3. The method of claim 1 , wherein the removing comprises washing the precipitated catalyst with water.

4. The method of claim 1 , wherein the purified catalyst is about 95 wt% pure to about 100 wt% pure.

5. The method of claim 1 , wherein axial ligand L is chosen from MeOH and H 2 O.

6. The method of claim 1 , wherein at one more occurrences at least one of R 2 , R 3 , R 4 , and R 5 is a hydrophilic group, wherein at each occurrence, the hydrophilic group is chosen from —C(O)OH, —O—C(O)OH, —P(O)(OH) 2 , —OP(O)(OH) 2 , —S(O)(O)OH, —OS(O)(O)OH, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof.

7. The method of claim 1 , wherein at one more occurrences at least one of R 2 , R 3 , R 4 , and R 5 is —S(O)(O)OH.

8. The method of claim 1 , wherein the catalyst has the structure:

wherein axial ligand L is H 2 O.

9. The method of claim 1 , wherein the catalyst composition further comprises a secondary catalyst, wherein the secondary catalyst has a different structure than the catalyst, wherein the secondary catalyst has the structure:

wherein
M is a metal,
axial ligand L is a solvent molecule,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, and a hydrophilic group.

10. The method of claim 9 , wherein the secondary catalyst has the structure:

wherein axial ligand L is MeOH.

11. A purified catalyst having the structure:

wherein
M is a metal,
axial ligand L is a solvent molecule,
at each occurrence, R A and R B are independently chosen from —H, halide, an organic group, and a hydrophilic group, or R A and R B together form a fused aromatic ring with the ring upon which R A and R B are substituted, R A and R B together having the structure:

at each occurrence, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently chosen from —H, halide, an organic group, and a hydrophilic group, wherein at each occurrence, the hydrophilic group is independently chosen from —C(O)OH, —O—C(O)OH, —P(O)(OH) 2 , —OP(O)(OH) 2 ,—S(O)(O)OH, —OS(O)(O)OH, a salt thereof, a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl ester thereof, and a combination thereof, and
the purified catalyst is about 95 wt% pure to about 100 wt% pure.

12. The purified catalyst of claim 11 , wherein axial ligand L, is chosen from MeOH and H 2 O.

13. The purified catalyst of claim 11 , wherein at one more occurrences at least one of R 2 , R 3 , R 4 , and R 5 is —S(O)(O)OH.

14. The purified catalyst of claim 11 , wherein the catalyst has the structure:

wherein axial ligand L is H 2 O.

15. A method of oxidation, comprising:
contacting an oxidizable starting material with the catalyst of claim 11 and an oxidant, to provide an oxidized product, wherein the oxidizable starting material is a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl alcohol.

16. A catalyst having the structure:

wherein
M is a metal,
L is a solvent molecule, and
at each occurrence, R 1 ,R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from —H, halide, an organic group, and a hydrophilic group.

17. A method of oxidation, comprising:
contacting an oxidizable starting material with the catalyst of claim 16 and an oxidant , to provide an oxidized product, wherein the oxidizable starting material is a substituted or unsubstituted (C 1 -C 50 )hydrocarbyl alcohol.

18. The method of claim 17 , wherein the contacting to provide an oxidized product is carried out under solvent-free conditions.

19. The purified catalyst of claim 11 , wherein at least one of R A , R B , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a hydrophilic group.

Assignees

• Wisys Tech Foundation Inc

Inventors

• Mcgaff Robert William

Classifications

• B01J2231/763

  of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species · CPC title

• C07C45/29

  of hydroxy groups · CPC title

• C07C45/294

  with hydrogen peroxide · CPC title

• B01J31/1835

  comprising aliphatic or saturated rings · CPC title

• C07F15/025 Primary

  without a metal-carbon linkage · CPC title