14172-92-0

Usage

Chemical Properties

dark purple crystalline powder or crystals

Purification Methods

Purify it by chromatography on neutral (Grade I) alumina, followed by recrystallisation from CH2Cl2/MeOH [Yamashita J Phys Chem 91 3055 1987]. [Beilstein 26 III/IV 1960.]

InChI:InChI=1/C44H30N4.Ni/c1-5-13-29(14-6-1)38-27-37-26-35-22-21-33(45-35)25-34-23-24-36(46-34)28-39-40(30-15-7-2-8-16-30)41(31-17-9-3-10-18-31)44(48-39)42(43(38)47-37)32-19-11-4-12-20-32;/h1-28,45,48H;/q;+2/b33-25-,34-25-,35-26-,36-28-,37-26-,39-28-,43-42-,44-42-;

Upstream product

• 917-23-7 5,10,15,20-tetraphenyl-21H,23H-porphine 
• 6018-89-9 nickel(II) acetate tetrahydrate 
• 88669-50-5 nickel-tetraphenylporphyrin^(1-) 
• 99685-96-8 fullerene-C₆₀ 
• 373-02-4 nickel diacetate 
• 55835-67-1 Ni(meso-5,10,15-20-tetraphenylporphyrinate)(piperidine)2 
• 101056-27-3 Ni(tetraphenylporphyrin)(pyridine)2 
• 14100-15-3 nickel(II) 8-hydroxyquinolate 
• 161927-78-2 [nickel(III)(tetraphenylporphyrin)(CH₃CN)2]⁽¹⁺⁾ 
• 162071-64-9 [nickel(III)(tetraphenylporphyrin)(CN)2]^(1-) 
• 161927-77-1 [nickel(III)(tetraphenylporphyrin)(pyridine)2]⁽¹⁺⁾ 
• 161927-76-0 [nickel(III)(tetraphenylporphyrin)(tetrahydrofuran)2]⁽¹⁺⁾ 
• 917-23-7 5,15,10,20-tetraphenylporphyrin 
• 83864-14-6 nickel dichloride 

Downstream Products

• 131214-90-9 [2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato]nickel 
• 95212-88-7 nickel(II) 2-nitro-5,10,15,20-tetraphenylporphyrinate 
• 554432-99-4 [Ni(II)tetraphenylporphyrin](dibuthylamine)2 
• 189874-29-1 2,7,12,17-tetrachloro-5,10,15,20-tetraphenylporphyrinatonickel(II) 
• 88669-50-5 nickel-tetraphenylporphyrin^(1-) 
• 554432-91-6 [Ni(II)tetraphenylporphyrin](diethylamine)2 
• 554432-85-8 Ni(C₄₄H₂₈N₄)(C₃H₇NH₂)2 
• 554432-95-0 Ni(C₄₄H₂₈N₄)(C₄H₉NH₂)2 
• 554432-98-3 [Ni(II)tetraphenylporphyrin](dipropylamine)2 
• 554432-90-5 [Ni(II)tetraphenylporphyrin](4-methylpyridine)2 
• 554432-88-1 [Ni(II)tetraphenylporphyrin](3-trimethylpyridine)2 
• 52588-71-3 2,7,12,17-tetrabromo-5,10,15,20-tetraphenylporphyrinatonickel(II) 
• 131214-90-9 (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)nickel(II) 
• 554432-96-1 Ni(C₄₄H₂₈N₄)(C₃H₇NH₂)2 

Relevant academic research and scientific papers

Probing transient molecular structures with time-resolved pump/probe XAFS using synchrotron X-ray sources

Laser pulse pump, X-ray pulse probe X-ray absorption fine structure (pump-probe XAFS) experiments using synchrotron sources are described from technical considerations and from scientific significance. There are three technical challenges of such experiments: (1) laser photoexcitation, (2) synchronization of laser pulse and X-ray pulse, and (3) detection; each of which is investigated in detail. Based on the results from these investigations, the transient molecular structure of a reaction intermediate produced by photoexcitation of NiTPP-L2 (NiTPP, nickeltetraphenylporphyrin; L, piperidine) in solution has been captured for the first time with the pump-probe XAFS on a 14-ns time scale obtained from the X-ray pulses from a third generation synchrotron source. The experimental results confirm that photoexcitation leads to the rapid removal of both axial ligands to produce a transient square-planar intermediate, NiTTP, with a lifetime of 28 ns. The transient structure of the photodissociated intermediate is nearly identical to that of the ground state NiTPP, suggesting that the intermediate adopts the same structure as the ground state in a non-coordinating solvent before it recombines with two ligands to form the more stable octahedrally coordinated NiTPP-L2. No detectable population of a penta-coordinated intermediate was present. This experiment demonstrates the feasibility of determining transient molecular structures in disordered media using the temporal resolution of a synchrotron X-ray source.

The breaking and mending of porphyrins: Reductive coupling of secochlorin bisaldehydes

The reaction of free base or Ni(II) complex secochlorin bisaldehydes 4H2 and 4Ni regenerates the ultimate starting material of the bisaldehydes, meso-tetraphenylporphyrin 2H2 and 2Ni, respectively. Depending on the reaction conditions employed (hydrazine hydrate in pyridine at reflux or hydrazine hydrate activated with sulfur in the presence of aqueous NaOH at ambient temperature), either porphyrin 2H2 is formed together with known dihydroxymorpholinochlorin 9H2 or known 2-hydroxychlorin 8H2. Two different reaction pathways for the hydrazine reaction can be derived, either involving the formation of a meso-tetraphenyl-1,4,5- triazepinoporphyrin that loses spontaneously N2 or a Wolff-Kishner-type pathway that also involves an intramolecular aldol-type reaction. Neither reaction is synthetically useful but both highlight in an impressive fashion the high thermodynamic stability of porphyrins. They also bring the 'breaking and mending of porphyrin' strategy to its ultimate conclusion by regenerating the starting porphyrin.

Insertion of Ni(I) into Porphyrins at Room Temperature: Preparation of Ni(II)porphyrins, and Ni(II)chlorins and Observation of Hydroporphyrin Intermediates

Reduced Nickel porphyrins play an important role as enzymatic cofactors in the global carbon cycle (cofactor F430), and as powerful catalysts in solar-to-fuel-processes such as the hydrogen evolution reaction, and the reduction of CO and CO2. The preparation of Ni(II)porphyrins requires harsh conditions, and characterization of the reduced species is intricate. We present a very mild, convenient, and high yielding method of inserting Ni into electron rich, and electron deficient porphyrins which at the same time gives access to to Ni(II) phlorins and Ni(II)chlorins and Ni(II)porphyrins.

Identification of Single-Atom Ni Site Active toward Electrochemical CO2Conversion to CO

Electrocatalytic conversion of CO2 into value-added products offers a new paradigm for a sustainable carbon economy. For active CO2 electrolysis, the single-atom Ni catalyst has been proposed as promising from experiments, but an idealized Ni-N4 site shows an unfavorable energetics from theory, leading to many debates on the chemical nature responsible for high activity. To resolve this conundrum, here we investigated CO2 electrolysis of Ni sites with well-defined coordination, tetraphenylporphyrin (N4-TPP) and 21-oxatetraphenylporphyrin (N3O-TPP). Advanced spectroscopic and computational studies revealed that the broken ligand-field symmetry is the key for active CO2 electrolysis, which subordinates an increase in the Ni redox potential yielding NiI. Along with their importance in activity, ligand-field symmetry and strength are directly related to the stability of the Ni center. This suggests the next quest for an activity-stability map in the domain of ligand-field strength, toward a rational ligand-field engineering of single-atom Ni catalysts for efficient CO2 electrolysis.

Efficient oxidation of cumene to cumene hydroperoxide with ambient O2 catalyzed by metalloporphyrins

A novel and efficient protocol for oxidation of cumene to cumene hydroperoxide was presented using ambient O2 catalyzed by very simple metalloporphyrins. The selectivity toward cumene hydroperoxide reached 98.3% in the cumene conversion of 28.1% with T(4-COOH)PPCu as a catalyst at 80°C. The origin of the higher performance of T(4-COOH)PPCu was mainly ascribed to the low catalytic performance of copper(II) in the cumene hydroperoxide decomposition, and the ability of T(4-COOH)PP in stabilizing cumene hydroperoxide through hydrogen-bond interactions between them. Compared with current industrial processes and academic research in oxidation of cumene to cumene hydroperoxide with O2, the main superiorities of this protocol were the high selectivity, high conversion, simple catalysts, solvent-free, additive-free and mild conditions which made this work an appealing reference for the industrial oxidation of cumene to cumene hydroperoxide, as well as the oxidative functionalization of other C-H bonds in various hydrocarbons. 2021 World Scientific Publishing Company.

Effect of degree of β-chlorination on photocatalytic activity of meso-tetraphenylporphyrin under homogeneous and nanoscale heterogeneous conditions: Chlorination vs. bromination

β-Chlorination of meso-tetraphenylporphyrin, H2TPP leads to the formation of H2TPPClx (X = 2, 4, 6 and 8) with absorption bands in the range of 421–451 and 650–715 nm, for the Soret and Q(0,0) bands, respectively. H2

Partial and full β-bromination of meso-tetraphenylporphyrin: Effects on the catalytic activity of the manganese and nickel complexes for photo oxidation of styrene in the presence of molecular oxygen and visible light

A series of β-brominated meso-tetraphenylporphyrins, H2TPPBrx (x = 0, 4, 8) have been synthesized and the photocatalytic activity of their manganese (III) and nickel (II) complexes in photo oxidation of styrene was thoroughly investi

Synthesis method of tetraaryl nickel porphyrin catalyzed by anhydrous aluminum trichloride

The invention discloses a synthesis method of tetraaryl nickel porphyrin catalyzed by anhydrous aluminum trichloride, which comprises the following step: refluxing aromatic aldehyde, pyrrole and nickel salt in a DMF solvent under the catalysis of anhydrous aluminum trichloride to synthesize tetraaryl nickel porphyrin in one step. The reaction process comprises the following steps: sequentially adding anhydrous aluminum trichloride, aryl aldehyde, pyrrole and nickel salt into DMF (Dimethyl Formamide) while stirring, stopping the reaction after heating reflux reaction for a certain time, cooling, standing overnight near 273K, and carrying out suction filtration to obtain a nickel porphyrin crystal. According to the method, aromatic aldehyde, pyrrole and nickel salt are directly used as raw materials, porphin is not needed, strongly corrosive organic acid is not used as a solvent, high-purity tetraaryl nickel porphyrin is obtained at a high yield under the condition that a complex separation means is not needed, and industrial production is easy to achieve.

Nickel(II) Tetraphenylporphyrin as an Efficient Photocatalyst Featuring Visible Light Promoted Dual Redox Activities

Nickel(II) tetraphenylporphyrin (NiTPP) is presented as a robust, cost-effective and efficient visible light induced photoredox catalyst. The ground state electrochemical data (CV) and electronic absorption (UV-Vis) spectra reveal the excited state redox potentials for [NiTPP]*/[NiTPP].? and NiTPP].+/[NiTPP]* couples as +1.17 V and ?1.57 V vs SCE respectively. The potential values represent NiTPP as a more potent photocatalyst compare to the well-explored [Ru(bpy)3]2+. The non-precious photocatalyst exhibits excited state redox reactions in dual fashions, i. e., it is capable of undergoing both oxidative as well as reductive quenching pathways. Such versatility of a photocatalyst based on first-row transition metals is very scarce. This unique phenomenon allows one to perform diverse types of redox reactions by employing a single catalyst. Two different sets of chemical reactions have been performed to represent the synthetic utility. The catalyst showed superior efficiency in both carbon-carbon and carbon-heteroatom bond-forming reactions. Thus, we believe that NiTPP is a valuable addition to the photocatalyst library and this study will lead to more practical synthetic applications of earth-abundant-metal-based photoredox catalysts. (Figure presented.).

Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins

Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.