Metal complexation of 1-acyldipyrromethanes and porphyrins formed therefrom
A first aspect of the invention is a method of making a porphyrin-metal complex, comprising: (a) providing a first reagent selected from the group consisting of 1-acyldipyrromethanes, 1-acyldipyrrins, dipyrromethane-1-carbinols 1,9-diacyldipyrromethanes and 1,9-diacyldipyrrins; and then (b) condensing the first reagent with either itself (in the case of 1-acyldipyrromethanes, 1-acyldipyrrins, and dipyrromethane-1-carbinols) or a dipyrromethane (in the case of 1,9-diacyldipyrromethanes and 1,9-diacyldipyrrins) in a reaction mixture comprising a solvent and a second reagent selected from the group consisting of palladium and copper complexes to produce the porphyrin-metal complex (with the metal being palladium or copper). In preferred embodiments of the foregoing, the reaction mixture further comprises a base such as KOH or NaH.
1. A method of making a porphyrin-metal complex, comprising:
(a) providing a first reagent selected from the group consisting of 1-acyldipyrromethanes, 1-acyldipyrrins, and dipyrromethane-1-carbinols; and then
(b) condensing said first reagent with itself in a reaction mixture comprising a solvent and a second reagent selected from the group consisting of palladium and copper complexes to produce a porphyrin-metal complex, wherein said metal is selected from the group consisting of palladium and copper.
2. The method of claim 1 , wherein said first reagent is a 1-acyldipyrromethane.
3. The method of claim 1 , wherein said first reagent is a 1-acyldipyrrin.
4. The method of claim 1 , wherein said first reagent is a dipyrromethane-1-carbinol.
5. The method of claim 1 , wherein said second reagent is a copper 0, copper I, copper II, or copper III complex.
6. The method of claim 1 , wherein said second reagent is a palladium 0, palladium II, or palladium IV complex.
7. The method of claim 1 , wherein said second reagent is a palladium II or palladium IV complex.
8. The method of claim 1 , wherein said second reagent is a palladium II or palladium IV complex selected from the group consisting of PdX 2 , PdX 2 L 2 , PdX 2 L 4 , and PdX 4 Y 2 Z 2 , wherein X is an anion, L is a neutral group; Y is a cation, and Z is an anion.
9. The method of claim 1 , wherein said second reagent is a palladium II or palladium IV complex selected from the group consisting of: K 2 PdCl 6 , Na 2 PdCl 6 , (NH 4 ) 2 PdCl 6 , Pd(OAc) 2 , Pd(acac) 2 , PdCl 2 , PdBr 2 , Pd(CN) 2 , PdI 2 , PdO, PdO.xH 2 O, PdS, Pd(O 2 CCF 3 ) 2 , C 3 H 5 PdCl 2 , (NH 4 ) 2 PdCl 4 , Pd(NO 3 ) 2 .xH 2 O, PdSO 4 .H 2 O, K 2 PdBr 4 , K 2 PdCl 4 , Na 2 PdCl 4 , K 2 Pd(S 2 O 3 ) 2 .H 2 O, (CH 3 CO 2 ) 2 Pd[P(C 6 H 5 ) 3 ] 2 , Pd(NH 3 ) 2 (NO 2 ) 2 , Pd(NH 3 ) 2 (NO 3 ) 2 , [Pd(NH 3 ) 4 ][Pd Cl 4 ], Pd(NH 3 ) 2 Cl 2 , PdCl 2 (CH 3 CN) 2 , PdCl 2 [P(C 6 H 5 ) 3] 2 , PdCl 2 (C 6 H 5 CN) 2 , Pd(O 2 CC 2 C 2 H 5 ) 2 , Pd Cl 2 [P(C 6 H 11 ) 3 ] 2 , PdCl 2 [P(C 6 H 5 ) 3 ] 2 , PdCl 2 [P(CH 3 C 6 H 5 ) 3] 2 , Pd(BF 4 ) 2 (CH 3 CN) 4 , trans-di(μ-acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium, dichloro(1,2-bis(diphenylphosphino)ethane)palladium(II), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II)dichloromethane adduct, palladium(II)hexafluoroacetylacetonate, dichloro(1,5-cyclooctadiene)palladium(II), ammonium bis(oxalato)palladium(II), dichloro(ethylenediamine)palladium(II), bis(pyridine)palladium(II)chloride, chloro(di-2-norbornylphosphino)(2-dimethylaminomethylferrocen-1-yl)palladium(II), chloro(di-2-norbornylphosphino)(2′-dimethylamino-1,1′-biphenyl-2-yl)palladium(II), dichloro(1,3-bis(diphenylphosphino)propane)palladium(II), bis[tris(4-(1H, 1H,2H,2H-perfluorodecyl)phenyl)phosphine]palladium(II)dichloride, benzylbis(triphenylphosphine)palladium(II)chloride, (bicyclo[2.2.1]hepta-2,5-diene)dichloropalladium(II), ([2S,3S]-bis[diphenylphosphino]butane)(eta 3 -allyl)palladium(II)perchlorate, acetato(2′-di-t-butylphosphino-1,1′-biphenyl-2-yl)palladium(II), allylchloro[1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene]palladium(II).
10. The method of claim 1 , wherein said second reagent is selected from the group consisting of Pd(OAc) 2 , Pd(acac) 2 , Pd(CH 3 CN) 2 Cl 2 , PdBr 2 and PdCl 2 .
11. The method of claim 1 , wherein said solvent is an alcohol solvent, ethereal solvent, tetrahydrofuran, water, or mixture thereof.
12. The method of claim 1 , wherein said solvent is ethanol.
13. The method of claim 1 , wherein said reaction mixture further comprises a base.
14. The method of claim 1 , wherein said reaction mixture further comprises a base selected from the group consisting of KOH and NaH.
15. The method of claim 1 , wherein said reaction mixture has a pH of at least 7.
16. The method of claim 1 , wherein said reaction mixture comprises not more than 0.5 percent by weight added acid.
17. The method of claim 1 , wherein said condensing step is carried out in the presence of an oxidizing agent.
18. The method of claim 1 ,wherein said condensing step is carried out in the presence of an oxidizing agent, and wherein said oxidizing agent is ambient oxygen.
19. The method of claim 1 , wherein said condensing step is carried out at a temperature of 0 to 150° C.
20. The method of claim 1 , wherein said condensing step is carried out for a time of 1 minute to 1 hour.
21. A method of making a porphyrin-metal complex, comprising:
(a) providing a first reagent selected from the group consisting of 1,9-diacyldipyrromethanes and 1,9-diacyldipyrrins; and then
(b) condensing said first reagent with a dipyrromethane in a reaction mixture comprising an solvent and a a second reagent selected from the group consisting of palladium and copper complexes to produce a porphyrin-metal complex, wherein said metal is selected from the group consisting of palladium and copper.
22. The method of claim 21 , wherein said first reagent is a 1,9-diacyldipyrromethane.
23. The method of claim 21 , wherein said first reagent is a 1,9-diacyldipyrrin.
24. The method of claim 21 , wherein said second reagent is a copper 0, copper I, copper II, or copper III complex.
25. The method of claim 21 , wherein said second reagent is a palladium 0, palladium II, or palladium IV complex.
26. The method of claim 21 , wherein said second reagent is a palladium II or palladium IV complex.
27. The method of claim 21 , wherein said second reagent is a palladium II or palladium IV complex selected from the group consisting of PdX 2 , PdX 2 L 2 , PdX 2 L 4 , and PdX 4 Y 2 Z 2 , wherein X is an anion, L is a neutral group; Y is a cation, and Z is an anion.
28. The method of claim 21 , wherein said second reagent is a palladium II or palladium IV complex selected from the group consisting of: K 2 PdCl 6 , Na 2 PdCl 6 , (NH 4 ) 2 PdCl 6 , Pd(OAc) 2 , Pd(acac) 2 , PdCl 2 , PdBr 2 , Pd(CN) 2 , PdI 2 , PdO, PdO.xH 2 O, PdS, Pd(O 2 CCF 3 ) 2 , C 3 H 5 PdCl 2 , (NH 4 ) 2 PdCl 4 , Pd(NO 3 ) 2 .xH 2 O, PdSO 4 .H 2 O, K 2 PdBr 4 , K 2 PdCl 4 , Na 2 PdCl 4 , K 2 Pd(S 2 O 3 ) 2 .H 2 O, (CH 3 CO 2 ) 2 Pd[P(C 6 H 5 ) 3 ] 2 , Pd(NH 3 ) 2 (NO 2 ) 2 , Pd(NH 3 ) 2 (NO 3 ) 2 , [Pd(NH 3 ) 4 ][PdCl 4 ], Pd(NH 3 ) 2 Cl 2 , PdCl 2 (CH 3 CN) 2 , PdCl 2 [P(C 6 H 5 ) 3 ] 2 , PdCl 2 (C 6 H 5 CN) 2 , Pd(O 2 CC 2 C 2 H 5 ) 2 , PdCl 2 [P(C 6 H 11 ) 3 ] 2 , PdCl 2 [P(C 6 H 5 ) 3 ] 2 , PdCl 2 [P(CH 3 C 6 H 5 ) 3 ] 2 , Pd(BF 4 ) 2 (CH 3 CN) 4 , trans-di(μ-acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium, dichloro(1,2-bis(diphenylphosphino)ethane)palladium(II), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II)dichloromethane adduct, palladium(II)hexafluoroacetylacetonate, dichloro(1,5-cyclooctadiene)palladium(II), ammonium bis(oxalato)palladium(II), dichloro(ethylenediamine)palladium(II), bis(pyridine)palladium(II)chloride, chloro(di-2-norbornylphosphino)(2-dimethylaminomethylferrocen-1-yl)palladium(II), chloro(di-2-norbornylphosphino)(2′-dimethylamino-1,1′-biphenyl-2-yl)palladium(II), dichloro(1,3-bis(diphenylphosphino)propane)palladium(II), bis[tris(4-(1H, 1H,2H,2H-perfluorodecyl)phenyl)phosphine]palladium(II)dichloride, benzylbis(triphenylphosphine)palladium(II)chloride, (bicyclo[2.2.1]hepta-2,5-diene)dichloropalladium(II), ([2S,3 S]-bis[diphenylphosphino]butane)(eta 3 -allyl)palladium(II) perchlorate, acetato(2′-di-t-butylphosphino-1,1′-biphenyl-2-yl)palladium(II), allylchloro[1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene]palladium(II).
29. The method of claim 21 , wherein said second reagent is selected from the group consisting of Pd(OAc) 2 , Pd(acac) 2 , Pd(CH 3 CN) 2 Cl 2 , PdBr 2 and PdCl 2 .
30. The method of claim 21 , wherein said solvent is an alcohol solvent, ethereal solvent, tetrahydrofuran, water, or mixture thereof.
31. The method of claim 21 , wherein said solvent is ethanol.
32. The method of claim 21 , wherein said reaction mixture further comprises a base.
33. The method of claim 21 , wherein said reaction mixture further comprises a base selected from the group consisting of KOH and NaH.
34. The method of claim 21 , wherein said reaction mixture has a pH of at least 7.
35. The method of claim 21 , wherein said reaction mixture comprises not more than 0.5 percent by weight added acid.
36. The method of claim 21 , wherein said condensing step is carried out in the presence of an oxidizing agent.
37. The method of claim 21 , wherein said condensing step is carried out in the presence of an oxidizing agent, and wherein said oxidizing agent is ambient oxygen.
38. The method of claim 21 , wherein said condensing step is carried out at a temperature of 0 to 150° C.
39. The method of claim 21 , wherein said condensing step is carried out for a time of 1 minute to 1 hour.