19414-65-4

Usage

Uses

Used in Chemical Research:
Meso-Tetratolylporphyrin-Co(II) is utilized as a catalyst in chemical reactions for its ability to facilitate processes that would otherwise be slow or inefficient. Its unique structure allows it to interact with a variety of reactants, making it a versatile component in the synthesis of complex organic and inorganic compounds.
Used in Industrial Applications:
In the industry, meso-Tetratolylporphyrin-Co(II) is employed as a catalyst to enhance the yield and selectivity of chemical reactions in the production of pharmaceuticals, agrochemicals, and other specialty chemicals. Its application contributes to more sustainable and efficient manufacturing processes.
Used in Biological Studies:
Meso-Tetratolylporphyrin-Co(II) serves as a vital tool in biological research, where it is used to study the interactions of metal ions with biological molecules. Its role in mimicking the active sites of metalloenzymes provides insights into their catalytic mechanisms and can aid in the development of new drugs and therapies.
Used in Photodynamic Therapy:
Although not explicitly mentioned in the provided materials, meso-Tetratolylporphyrin-Co(II), given its structural similarity to porphyrins used in photodynamic therapy, could potentially be used as a photosensitizer. In this application, it would be applied for its ability to absorb light and generate reactive oxygen species, which can be effective in the treatment of certain types of cancer and other diseases.

Upstream product

• 71-48-7 cobalt(II) acetate 
• 16940-66-2 sodium tetrahydroborate 
• 680-31-9 N,N,N,N,N,N-hexamethylphosphoric triamide 
• 34829-90-8 ((C₄H₂NC(p-MeC₆H₄))4)CoBr 
• 1605-65-8 N,N,N',N'-Tetramethylphosphorodiamidic chloride 
• 14527-51-6 5,10,15,20-tetra(p-tolyl)porphyrin 
• 104-87-0 4-methyl-benzaldehyde 
• 6147-53-1 cobalt(II) diacetate tetrahydrate 

Downstream Products

• 53536-91-7 Co(C₁₂H₉N)4O₂ 
• 65832-52-2 5,10,15,20-tetra-p-tolylporphyrinato(dimethylsulfoxide)cobalt(II) 
• 77743-32-9 Co(NC₄H₂CC₆H₄CH₃)4(C₃N₂H₃CH₃)2⁽¹⁺⁾*Cl^(1-)=[Co(NC₄H₂CC₆H₄CH₃)4(C₃N₂H₃CH₃)2]Cl 
• 80642-18-8 Co(CH₃C₆H₄)4C₂₀H₈N₄SCN 
• 34829-90-8 ((C₄H₂NC(p-MeC₆H₄))4)CoBr 
• 80642-19-9 Co(CH₃C₆H₄)4C₂₀H₈N₄N₃ 

Relevant academic research and scientific papers

Synthesis and Properties of N,N'- and Co,N'-Vinylene Linked Bisporphyrins

Bis(aquo)tetra(p-tolyl)porphinatocobalt(III) perchlorate reacted immediately with acetylene, in the absence and presence of tetra(p-tolyl)porphinatocobalt(II), to give a N,N'-vinylene linked bisporphyrin biscobalt(II) complex and a Co,N'-vinylene linked bisporphyrin cobalt(III) complex (4b), respectively. 4b was oxidatively converted into N,N'-vinylene linked bisporphyrin free base.An octaethylporphyrin analogue corresponding to 4b was obtained when a mixture of bis(aquo)octaethylporphyrinatocobalt(III) perchlorate and octaethylporphyrin was allowed to react with acetylene gas.

A porphyrin with a C=C unit at its center

The molecule (C=C)TTP (TTP = tetra-p-tolylporphyrin) and the triflate salt of its dication, [(C=C)TTP][OTf]2, have been synthesized and characterized. NMR spectroscopy, nucleus-independent chemical shift calculations, and the crystal structure of (C=C)TTP indicate that (C=C)TTP is antiaromatic and (C=C)TTP2+ is aromatic.

Reaction, structure and spectroscopic properties of bis(cyano) cobalt(III) porphyrin complexes

Cyanocobalamin and analogues have drawn much attention for the promising applications in photovoltaic and photocatalytic systems. In this study, two low spin bis(cyano) cobalt(III) porphyrin complexes [K(222)][CoIII(TPP)(CN)2] and [K(222)][CoIII(TMP)(CN)2] (222 = 4,7,13,16,21,24-hexaoxo-1,10-diazabicyclo[8.8.8]hexacosane, TPP = meso-tetraphenylporphyrin dianion, TMP = meso-tetramesitylporphyrin dianion), which were isolated from the reactions between [CoII(Porph)] (Porph = Porphyrin) and [K(222)(CN)], are characterized by a single crystal X-ray diffraction, FT-IR and UV-vis spectroscopies. Combined UV-vis and electron paramagnetic resonance (EPR) investigations have been conducted to understand the reaction mechanisms. The work gives new insights into the reactivities and spectroscopic properties of cyano cobalt macrocyclic complexes.

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.

Donor-acceptor conjugates derived from cobalt porphyrin and fullerene via metal-ligand axial coordination: Formation and excited state charge separation

Two types of cobalt porphyrins, viz., meso-tetrakis(tolylporphyrinato)cobalt(II), (TTP)Co (1), and meso-tetrakis(triphenylamino porphyrinato)cobalt(II), [(TPA)4P]Co, (2) were self-assembled via metal-ligand axial coordination of phenyl imidazole functiona

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.].

Efficient and selective oxidation of tertiary benzylic C[sbnd]H bonds with O2 catalyzed by metalloporphyrins under mild and solvent-free conditions

The direct and efficient oxidation of tertiary benzylic C[sbnd]H bonds to alcohols with O2 was accomplished in the presence of metalloporphyrins as catalysts under solvent-free and additive-free conditions. Based on effective inhibition on the unselective autoxidation and deep oxidation, systematical investigation on the effects of porphyrin ligands and metal centers, and apparent kinetics study, the oxidation system employing porphyrin manganese(II) (T(2,3,6-triCl)PPMn) with bulkier substituents as catalyst, was regarded as the most promising and efficient one. For the typical substrate, the conversion of cumene could reach up to 57.6% with the selectivity of 70.5% toward alcohol, both of them being higher than the current documents under similar conditions. The superiority of T(2,3,6-triCl)PPMn was mainly attributed to its bulkier substituent groups preventing metalloporphyrins from oxidative degradation, its planar structure favoring the interaction between central metal with reactants, and the high efficiency of Mn(II) in the catalytic transformation of hydroperoxides to alcohols.

Cobalt Tetrabutano- and Tetrabenzotetraarylporphyrin Complexes: Effect of Substituents on the Electrochemical Properties and Catalytic Activity of Oxygen Reduction Reactions

Three series of cobalt tetraarylporphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds have the general formula (TpYPP)Co, butano(TpYPP)CoII, and benzo(TpYPP)CoII, where TpYPP represents the dianion of the meso-substituted porphyrin, Y is a CH3, H, or Cl substituent on the para position of the four phenyl rings, and butano and benzo are respectively the β- and β′-substituted groups on the four pyrrole rings of the compound. Each porphyrin undergoes one or two reductions depending upon the meso substituent and solvent utilized. Two irreversible reductions are observed for (TpYPP)CoII and butano(TpYPP)CoII in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate; the first leads to the formation of a highly reactive cobalt(I) porphyrin, which can then rapidly react with a solvent to give a CoIIICH2Cl as the product. Only one reversible reduction is seen for benzo(TpYPP)CoII under the same solution conditions, and the one-electron-reduction product is assigned as a cobalt(II) porphyrin π-anion radical. Three oxidations can be observed for each examined compound in CH2Cl2. The first oxidation is metal-centered for the (TpYPP)Co and benzo(TpYPP)CoII derivatives, leading to generation of a cobalt(III) porphyrin with an intact π-ring system, but this redox process is ring-centered in the case of butano(TpYPP)CoII and gives a CoII π-cation radical product. Each porphyrin was also examined as a catalyst for oxygen reduction reactions (ORRs) when adsorbed on a graphite electrode in 1.0 M HClO4. The number of electrons transferred (n) during ORRs is 2.0 for the butano(TpYPP)CoII derivatives, consistent with only H2O2 being produced as a product for the reaction with O2. However, the reduction of O2 using the cobalt benzoporphyrins as catalysts gave n values between 2.6 and 3.1 under the same solution conditions, thus producing a mixture of H2O and H2O2 as the reduction product. This result indicates that the β and β′ substituents have a significant effect on the catalytic properties of the cobalt porphyrins for ORRs in acid media.

Cobalt Porphyrin-Polypyridyl Surface Coatings for Photoelectrosynthetic Hydrogen Production

Hybrid materials that link light capture and conversion technologies with the ability to drive reductive chemical transformations are attractive as components in photoelectrosynthetic cells. We show that thin-film polypyridine surface coatings provide a molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto a visible-light-absorbing p-type gallium phosphide semiconductor. Spectroscopic techniques, including grazing angle attenuated total reflection Fourier transform infrared spectroscopy, confirm that the cobalt centers of the porphyrin macrocycles coordinate to pyridyl nitrogen sites of the organic surface coating. The cobalt porphyrin surface concentration and fraction of pyridyl sites coordinated to a cobalt center are quantified using complementary methods of ellipsometry, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. In aqueous solutions under simulated solar illumination the modified cathode is photochemically active for hydrogen production, generating the product gas with near-unity Faradaic efficiency at a rate of ≈10 μL min-1 cm-2 when studied in a three-electrode configuration and polarized at the equilibrium potential of the H+/H2 couple. This equates to a photoelectrochemical hydrogen evolution reaction activity of 17.6 H2 molecules s-1 Co-1, the highest value reported to date for a molecular-modified semiconductor. Key features of the functionalized photocathode include (1) the relative ease of synthetic preparation made possible by application of an organic surface coating that provides molecular recognition sites for immobilizing the cobalt porphyrin complexes at the semiconductor surface and (2) the use of visible light to drive cathodic fuel-forming reactions in aqueous solutions with no added organic acids or sacrificial chemical reductants.

Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt(ii) porphyrins. the effect of the NO2 group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media

Four cobalt(ii) porphyrins, two of which contain a β-pyrrole nitro substituent, were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds are represented as (TRPP)Co and (NO2TRPP)Co, where TRPP is the dianion of a substituted tetraphenylporphyrin and R is a CH3 or OCH3 substituent on the four phenyl rings of the macrocycle. Two reductions and three oxidations are observed for each compound in CH2Cl2 containing 0.10 M tetra-n-butylammonium perchlorate. The first reduction of the compounds without a nitro substituent is metal-centered and leads to formation of a Co(i) porphyrin which then reacts with the CH2Cl2 solvent to generate a carbon σ-bonded CoIII-R complex. A further reduction then occurs at more negative potentials to generate an unstable Co(ii) σ-bonded compound. In contrast to these reactions, the first reduction of the nitro-substituted porphyrins is macrocycle-centered under the same solution conditions and gives a Co(ii) porphyrin π-anion radical product. This reversible electron transfer is then followed at more negative potentials by a second reversible one-electron addition to give a Co(ii) dianion. Three reversible one-electron oxidations are also seen for each compound. The first is metal-centered and the next two involve the conjugated π-system of the macrocycle. Each neutral Co(ii) porphyrin was also examined as to its catalytic activity for electroreduction of molecular oxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.