28903-71-1

Basic information

• Product Name: Cobalt tetramethoxyphenylporphyrin
• Synonyms: TMOPP-Co, 5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrine cobalt(II) Complex;Cobalt tetramethoxyphenylporphyrin,94%;[5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinato]cobalt(II);Cobalt (II) meso-tetramethoxyphe;Tetra(4-methoxyphenyl)porphyrine cobalt complex;Cobalt(II) meso-tetra(4-methoxyphenyl)porphine;2,4,5,20-tetraMethoxy-19-phenyl-21,22,23,24-tetraazapentacyclo[16.2.1.1^{3,6}.1^{8,11}.1^{13,16}]tetracosa-1,3,5,7,9,11(23),12,14,16,18(21),19-undecaene cobalt;Cobalt tetraMethoxyphenylporphyrin, 94% 1GR
• CAS NO: 28903-71-1
• Molecular Formula: C₄₈H₃₆CoN₄O₄
• Molecular Weight: 791.76
• EINECS: -0
• Product Categories: Transition Metal Compounds;CobaltPhotonic and Optical Materials;Catalysis and Inorganic Chemistry;Chemical Synthesis;Phthalocyanine and Porphyrin Dyes;Porphyrines;metal porphine (porphyrin) complex;Porphyrins;Biochemistry;Classes of Metal Compounds;Co (Cobalt) Compounds
• Mol File: 28903-71-1.mol
• Article Data: 14

Chemical Properties

• Melting Point: 241-248°C
• Appearance: Purple to violet/Crystals or Powder
• Storage Temp.: Sealed in dry,Room Temperature
• CAS DataBase Reference: Cobalt tetramethoxyphenylporphyrin(CAS DataBase Reference)
• NIST Chemistry Reference: Cobalt tetramethoxyphenylporphyrin(28903-71-1)
• EPA Substance Registry System: Cobalt tetramethoxyphenylporphyrin(28903-71-1)

Safety Data

• Safety Statements: 24/25
• WGK Germany: 3
• Hazardous Substances Data: 28903-71-1(Hazardous Substances Data)

Usage

Description

Cobalt tetramethoxyphenylporphyrin, also known as Arsenite Ionophore I (5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinatocobalt (TMOPP-Co)), is an organometallic complex derived from the synthesis of 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (TMOPP) and cobalt acetate in glacial acetic acid. It is characterized by its purple powder appearance and has a tendency to attract molybdate ions. This complex is known for its unique chemical properties and potential applications in various fields.

Uses

Used in Catalyst Applications:
Cobalt tetramethoxyphenylporphyrin is used as an oxidation catalyst in the chemical industry for a variety of synthetic reactions. One of its primary applications is in the selective oxidation of amines, which is crucial for the production of various chemicals and pharmaceuticals.
Used in Synthesis of Cobalt Nitrosyl Porphyrins:
In the field of bioinorganic chemistry, Cobalt tetramethoxyphenylporphyrin serves as a starting material in the synthesis of cobalt nitrosyl porphyrins. These synthesized compounds are used for studying the binding and activation of nitric oxide, which is essential for understanding various biological processes and developing potential therapeutic applications.
Used in Chemical Research:
Due to its unique chemical properties and tendency to attract molybdate ions, Cobalt tetramethoxyphenylporphyrin is also utilized in chemical research to explore new reaction pathways and develop novel synthetic methods. This contributes to the advancement of the chemical industry and the discovery of new compounds with potential applications in various sectors.

InChI:InChI=1/C48H36N4O4.Co/c1-53-33-13-5-29(6-14-33)45-37-21-23-39(49-37)46(30-7-15-34(54-2)16-8-30)41-25-27-43(51-41)48(32-11-19-36(56-4)20-12-32)44-28-26-42(52-44)47(40-24-22-38(45)50-40)31-9-17-35(55-3)18-10-31;/h5-28H,1-4H3;/q-2;+2/b45-37-,45-38-,46-39-,46-41-,47-40-,47-42-,48-43-,48-44-;

Synthetic route

cobalt(II) acetate (71-48-7, 917-69-1, 5931-89-5, 55881-15-7, 68931-68-0, 68931-69-1, 93029-27-7) + 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (22112-78-3) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In N,N-dimethyl-formamide at 110℃; for 1h; Inert atmosphere;	86%
In N,N-dimethyl-formamide for 0.00555556h; Reflux;	67%
In N,N-dimethyl-formamide at 150℃; for 24h; Inert atmosphere;
In N,N-dimethyl-formamide at 150℃; for 24h; Inert atmosphere;

5,10,15,20-meso-tetra(p-methoxyphenyl) porphyrin + cobalt(II) acetate (71-48-7, 917-69-1, 5931-89-5, 55881-15-7, 68931-68-0, 68931-69-1, 93029-27-7) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In N,N-dimethyl-formamide at 140℃; for 12h; Inert atmosphere;	59.4%
In acetic acid heating of tetra4-methoxy-phenyl)-prophine and Co(II)-acetate in acetic acid;; chromatographic purification with CHCl3 as solvent; recrystallisation in a CHCl3-CH3OH-mixture;;	33%
In acetic acid heating of tetra4-methoxy-phenyl)-prophine and Co(II)-acetate in acetic acid;; chromatographic purification with CHCl3 as solvent; recrystallisation in a CHCl3-CH3OH-mixture;;	33%

5,10,15,20-meso-tetra(p-methoxyphenyl) porphyrin + cobalt(II) diacetate tetrahydrate (6147-53-1) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In acetic acid porphyrin was added to boiling soln. of acetate in acetic acid, mixt. was boiled for 0.5 h and kept at room temp. for 12 h; ppt. was filtered, washed with hot water, dried in air at 70°C, chromd. (silica gel, chloroform), recrystd. from chloroform-hexane mixt.;	35%
In acetic acid mixt. of porphin, Co salt, acetic acid refluxed; cooled; filtered; ppt. washed (hot water); dried (air, 353 K); dissolvedin CHCl3; chromd. (Al2O3); eluate evapd. to min. vol.; pptd. (MeOH);

pyrrole (109-97-7) + 4-methoxy-benzaldehyde (123-11-5) + cobalt(II) chloride (7646-79-9) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In propionic acid in situ synthesis on RB-carbon support;	18%

5,10,15,20-meso-tetra(p-methoxyphenyl) porphyrin + cobalt(II) chloride (7646-79-9) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In N,N-dimethyl-formamide two step procedure: absorbing of metal chloride on RB-carbon carrier followed by reaction with porphin;	18%

4-methoxy-benzaldehyde (123-11-5) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: propionic acid; acetic acid; trifluoroacetic acid; nitrobenzene / 4 h / 140 °C 2: N,N-dimethyl-formamide / 12 h / 140 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: propionic acid / 2 h / 145 °C / Inert atmosphere; Darkness 2: N,N-dimethyl-formamide / 24 h / 150 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: propionic acid / 2.25 h / 140 °C / Inert atmosphere 2: N,N-dimethyl-formamide / 1 h / 110 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: propionic acid / 2 h / 145 °C / Inert atmosphere; Darkness 2: N,N-dimethyl-formamide / 24 h / 150 °C / Inert atmosphere View Scheme

C85H44CoF15N8O4Sn + oxygen (80937-33-3) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + C74H16F30N8OSn2

Conditions	Yield
In benzene-d6 under 760.051 Torr; Irradiation;

2,2,6,6-Tetramethyl-1-piperidinyloxy free radical (2564-83-2, 45842-10-2) + C85H44CoF15N8O4Sn → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + C37H8F15N4OSn

Conditions	Yield
In benzene-d6 at 70℃; Thermodynamic data; Inert atmosphere; Darkness;

cobalt(II) diacetate tetrahydrate (6147-53-1) + 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (22112-78-3) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
In N,N-dimethyl-formamide Reflux;

4-Methylanisole (104-93-8) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: oxygen; N-hydroxyphthalimide; cobalt(II) 5,10,15,20-tetra(o-methoxyphenyl)porphyrin complex / neat (no solvent) / 8 h / 120 °C / 7500.75 Torr / Autoclave 2: propionic acid / 2 h / 145 °C / Inert atmosphere; Darkness 3: N,N-dimethyl-formamide / 24 h / 150 °C / Inert atmosphere View Scheme

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (22112-78-3) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1)

Conditions	Yield
With aluminum oxide; lithium hydroxide for 0.666667h; Milling; Green chemistry;

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + ethyl iodide (75-03-6) → Co(C48H36N4O4)(C2H5)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In N,N-dimethyl-formamide excess AIBN and org. substrate, sealed tube (vac.), 333 K;	95%
With 2,2'-azobis(isobutyronitrile) In N,N-dimethyl-formamide a soln. of the Co-complex, the organic substrate and the azocompd. in DMF was sealed in an evacuated ampoule, heated at 60°C for 180-240 min; detected by H-NMR (>95 % yield);
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 300 min; detected by H-NMR (<2 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + 2-methyl-3-buten-2-ol (115-18-4) → Co(C48H36N4O4)(CH2CH2C(CH3)2OH)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In chloroform excess AIBN and org. substrate, sealed tube (vac.), 333 K;	95%
With 2,2'-azobis(isobutyronitrile) In chloroform Kinetics; a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 360-420 min; detected by H-NMR (>95 % yield);
With 2,2'-azobis(2,4-dimethylpentanenitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, react. at 25°C for 1800-2400 min; detected by H-NMR (>95 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → Co(C48H36N4O4)(CH3)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); methyl iodide In N,N-dimethyl-formamide excess AIBN and org. substrate, sealed tube (vac.), 333 K;	95%
With 2,2'-azobis(isobutyronitrile); methyl iodide In N,N-dimethyl-formamide a soln. of the Co-complex, the organic substrate and the azocompd. in DMF was sealed in an evacuated ampoule, heated at 60°C for 180-240 min; detected by H-NMR (>95 % yield);
With 2,2'-azobis(isobutyronitrile); methyl iodide In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 400 min; detected by H-NMR (5 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + carbon monoxide (201230-82-2) + 4-bromobenzenemethanol (873-75-6) → 4-bromobenzyloxycarbonylcobalt meso-(4-methoxyphenyl)porphyrin

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 20℃; under 5320.36 Torr; for 16h; Darkness;	94%

hydrogenchloride (7647-01-0) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + water (7732-18-5) → [5,10,15,20-tetra(p-methoxy)phenylporphyrin]cobalt(III) chloride monohydrate (158671-51-3)

Conditions	Yield
In methanol at 50℃; Inert atmosphere;	93%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + carbon monoxide (201230-82-2) + benzyl alcohol (100-51-6) → benzyloxycarbonylcobalt meso-(4-methoxyphenyl)porphyrin

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 20℃; under 5320.36 Torr; for 16h; Darkness;	93%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + carbon monoxide (201230-82-2) + 1-Phenylethanol (98-85-1, 13323-81-4) → 1-phenethyloxycarbonylcobalt meso-(4-methoxyphenyl)porphyrin

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 20℃; under 5320.36 Torr; for 16h; Darkness;	92%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + 2,4-dimethylpentan-3-one (565-80-0) → C52H43CoN4O5

Conditions	Yield
With water; triphenylphosphine In acetone at 25℃; for 1.5h; Darkness; Inert atmosphere;	89%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + ethanol (64-17-5) + carbon monoxide (201230-82-2) → ethoxycarbonylcobalt meso-(4-methoxyphenyl)porphyrin

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 20℃; under 5320.36 Torr; for 16h; Darkness;	87%

pyridine-4-carbonitrile (100-48-1) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + chloroform (67-66-3) → C54H40CoN6O4*CHCl3

Conditions	Yield
for 24h;	80%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + chloroform (67-66-3) + hexamethylenetetramine (100-97-0) → [CoII(TMPP)(HMTA)]•2CHCl3

Conditions	Yield
for 4h;	80%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + nitrogen(II) oxide (10102-43-9) → nitrolsylcobalt(II) meso-tetra(p-methoxyphenyl)porphyrin

Conditions	Yield
In dichloromethane absence of air and moisture; bubbling NO for 20 min; vol. reduction (boiling), pptn. on MeOH addn., decantation, drying (vac.), recrystn. (PhMe/hexane=10:1); elem. anal.;	72%
With piperidine In dichloromethane absence of air and moisture; excess piperidine, bubbling NO for 20 min; bubbling N2 for 2 min, vol. reduction (boiling), pptn. on MeOH addn., cooling to room temp., collection (filtration), washing (MeOH), recrystn. (CH2Cl2/hexane=1:1);	63%
With piperidine In dichloromethane Co-compd. dissoln., soln. degassing carefully, piperidine addn., NO bubbling into soln. for 0.5 h, NO excess removal on soln. purging with N2, heating to boiling, pptn. after MeOH addn.; ppt. filtration, vac. drying;	50%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + acrylic acid methyl ester (292638-85-8) → Co(C48H36N4O4)(CH(CH3)CO2CH3)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In chloroform excess AIBN and org. substrate, sealed tube (vac.), 333 K;	70%
With 2,2'-azobis(isobutyronitrile) In chloroform-d1 Kinetics; a soln. of the Co-complex, the organic substrate and the azocompd. in CDCl3 was sealed in an evacuated ampoule, heated at 60°C; detected by H-NMR;
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 90 min; detected by H-NMR (70 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + (Et4N)2[{Ni(κ2-SPh-o-NNO-p-CF3)(NO)}2] → nitrolsylcobalt(II) meso-tetra(p-methoxyphenyl)porphyrin + trans-(Et4N)2[Ni(SPh-o-NNO-p-CF3)2]

Conditions	Yield
In dichloromethane at 20℃; for 24h; Solvent;	A 70% B n/a

bromobenzene (108-86-1) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → C54H41CoN4O4 (571165-61-2)

Conditions	Yield
With potassium hydroxide; tert-butyl alcohol In benzene at 150℃; for 1.5h; Inert atmosphere; Darkness;	69%

ethyloxirane (106-88-7) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → Co(C48H36N4O4)(CH2CH(OH)C2H5)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In N,N-dimethyl-formamide excess AIBN and org. substrate, sealed tube (vac.), 333 K;	65%
With 2,2'-azobis(isobutyronitrile) In N,N-dimethyl-formamide a soln. of the Co-complex, the organic substrate and the azocompd. in DMF was sealed in an evacuated ampoule, heated at 60°C for 180-240 min; detected by H-NMR (65 % yield);
With 2,2'-azobis(2,4-dimethylpentanenitrile) In N,N-dimethyl-formamide Kinetics; a soln. of the Co-complex, the organic substrate and the azocompd. in DMF was sealed in an evacuated ampoule, react. at 40°C for 500-660 min; detected by H-NMR (84 % yield);
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 100-200 min; detected by H-NMR (<2 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + phenylacetylene (536-74-3) → Co(C48H36N4O4)(C(C6H5)CH2)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In chloroform excess AIBN and org. substrate, sealed tube (vac.), 333 K;	60%
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 80 min; detected by H-NMR (60 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + fullerene-C60 (99685-96-8, 161105-99-3, 161106-00-9, 111138-12-6, 133318-63-5, 134053-11-5, 134931-35-4, 134931-36-5, 139703-76-7, 145633-27-8, 175414-73-0, 175414-74-1, 175414-75-2, 175519-12-7, 175519-13-8, 175519-14-9, 175519-15-0, 136376-46-0, 144906-37-6, 144906-38-7, 151767-00-9, 152882-97-8, 152882-98-9, 152882-99-0, 153062-34-1, 154171-74-1, 154171-75-2, 154333-99-0, 154334-00-6, 154397-63-4, 154460-59-0, 199456-56-9, 108739-25-9, 120329-57-9, 120329-58-0) → (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II)*C60 (445241-52-1)

Conditions	Yield
With ferrocene In toluene a soln. in toluene containing Co-complex, C60 and ferrocene at a 1:1:10 molar ratio, was evapd. under Ar; the solvent was decanted, crystals were washed with dry acetone;	60%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → nitrolsylcobalt(II) meso-tetra(p-methoxyphenyl)porphyrin

Conditions	Yield
With [C5H10NH2](+)[C5H10NN(O)NO](-) In dichloromethane N2-atmosphere; stirring for 30 min, then boiling; pptn. on MeOH addn., cooling to room temp., collection (filtration), washing (MeOH), drying (vac.);	60%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + carbon monoxide (201230-82-2) + tert-butyl alcohol (75-65-0) → tert-butyloxycarbonylcobalt meso-(4-methoxyphenyl)porphyrin

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In toluene at 20℃; under 5320.36 Torr; for 16h; Darkness;	60%

styrene (292638-84-7) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → Co(C48H36N4O4)(CH(CH3)C6H5)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In chloroform excess AIBN and org. substrate, sealed tube (vac.), 333 K;	50%
With 2,2'-azobis(isobutyronitrile) In chloroform-d1 Kinetics; a soln. of the Co-complex, the organic substrate and the azocompd. in CDCl3 was sealed in an evacuated ampoule, heated at 60°C; detected by H-NMR;
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, heated at 60°C for 90-120 min; detected by H-NMR (47 % yield);

hydrogenchloride (7647-01-0) + (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) → 5,10,15,20-tetra(4-methoxyphenyl) porphyrinato cobalt chloride (82150-28-5)

Conditions	Yield
With air In hydrogenchloride; methanol air flow was passed through suspn. of Co(II) complex in MeOH and concd. HCl for 10 h; ppt. was filtered, soln. was neutralized by concd. soln. of NH4OH;	47%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + water (7732-18-5) + 2,3-dicyano-5,6-dichloro-p-benzoquinone (84-58-2) → C48H36CoN4O4(1+)*CN(1-)*H2O

Conditions	Yield
In chloroform at 20℃; for 2h;	0.6%

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + homoalylic alcohol (627-27-0) → Co(C20N4H8(C6H4OCH3)4)(CH2(CH2)3OH) + Co(C20N4H8(C6H4OCH3)4)(CH(CH3)(CH2)2OH)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, react. at 60°C for 120-150 min; detected by H-NMR (52/28 % yield);

(5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II) (28903-71-1) + homoalylic alcohol (627-27-0) → Co(C20N4H8(C6H4OCH3)4)(CH(CH3)(CH2)2OH)

Conditions	Yield
With 2,2'-azobis(2,4-dimethylpentanenitrile) In chloroform a soln. of the Co-complex, the organic substrate and the azocompd. in CHCl3 was sealed in an evacuated ampoule, react. at 40°C for 300-360 min; detected by H-NMR (>95 % yield);
With 2,2'-azobis(isobutyronitrile) In chloroform-d1 Kinetics; a soln. of the Co-complex, the organic substrate and the azocompd. in CDCl3 was sealed in an evacuated ampoule, react. at 60°C; detected by H-NMR;

Upstream product

• 109-97-7 pyrrole 
• 123-11-5 4-methoxy-benzaldehyde 
• 7646-79-9 cobalt(II) chloride 
• 104-93-8 p-methylanizole 
• 15226-74-1 dicobalt octacarbonyl 
• 22112-78-3 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin 
• 71-48-7 cobalt(II) acetate 
• 6147-53-1 cobalt(II) diacetate tetrahydrate 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 80937-33-3 oxygen 

Downstream Products

• 158671-51-3 [5,10,15,20-tetra(p-methoxy)phenylporphyrin]cobalt(III) chloride monohydrate 

Relevant articles and documents

Kinetic parameters of the electroreduction of oxygen on a graphitized carbon electrode activated by tetrakis(4-methoxyphenyl)porphyrin and its cobalt complexes

Electrochemical and electrocatalytic properties of tetrakis(4- methoxyphenyl)porphyrin, tetrakis(4-methoxyphenyl)porphyrinatocobalt(II), and (tetrakis(4-methoxyphenyl)porphyrinato)chlorocobalt(III) are studied using the method of cyclic voltammetry. The redox-potentials of the electrode processes, the potentials of the half-wave and stationary rate constants for electroreduction of molecular oxygen are determined from an analysis of the voltammetric curves. The cobalt complex is found to be characterized by higher electrocatalytic activity than other analyzed compounds.

Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids

The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.

Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide

Abstract: A protocol for solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts to overcome the deficiencies encountered in current oxidation systems. The effects of reaction temperature, porphyrin structure, central metal, catalyst loading and O2 pressure were investigated systematically. For the optimized combination of T(2-OCH3)PPCo and NHPI, all the primary benzylic C–H bonds could be functionalized efficiently and selectively at 120 °C and 1.0?MPa O2 with aromatic acids as the primary products. The selectivity towards aromatic acids could reach up to 70–95% in the conversion of more than 30% for most of the substrates possessing primary benzylic C–H bonds in the metalloporphyrin loading of 0.012% (mol/mol). And the superior performance of T(2-OCH3)PPCo among the metalloporphyrins investigated was mainly attributed to its high efficiency in charge transfer and fewer positive charges around central metal Co (II) which favored the adduction of O2 to cobalt (II) forming the high-valence metal-oxo complex followed by the production of phthalimide N-oxyl radical (PINO) and the initiation of the catalytic oxidation cycle. This work would provide not only an efficient protocol in utilization of hydrocarbons containing primary benzylic C–H bonds, but also a significant reference in the construction of more efficient C–H bonds oxidation systems. Graphic Abstract: The solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts, and the highest selectivity towards aromatic acid reached up to 95.1% with the conversion of 88.5% in the optimized combination of T(2-OCH3)PPCo and NHPI.[Figure not available: see fulltext.].