445487-66-1

Upstream product

• 6018-89-9 nickel(II) acetate tetrahydrate 
• 373-02-4 nickel diacetate 
• 25440-14-6 tetrakis(pentafluorophenyl)porphyrin 

Downstream Products

• 176172-86-4 Ni(C₂₀H₈N₄(C₆F₄O(CH₂)3NC₄H₄)(C₆F₅)3) 
• 176172-87-5 Ni(C₂₀H₈N₄(C₆F₄O(CH₂)3NC₄H₄)2(C₆F₅)2) 
• 176172-88-6 Ni(C₂₀H₈N₄(C₆F₄O(CH₂)3NC₄H₄)3(C₆F₅)) 
• 1253288-45-7 C₅₄H₁₆F₂₀N₈NiO₄ 
• 158051-26-4 [5,10,15,20-tetra(pentafluorophenyl)porpholactone]Ni(II) 

Relevant academic research and scientific papers

Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction

A nickel(II) porphyrin Ni-P (P=porphyrin) bearing four meso-C6F5 groups to improve solubility and activity was used to explore different hydrogen-evolution-reaction (HER) mechanisms. Doubly reduced Ni-P ([Ni-P]2-) was invo

Kinetics and mechanism for the metalation reaction of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin with diaquabis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)nickel(II) in supercritical carbon dioxide

The nickel(II) ion incorporation reaction into 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (H2tpfpp) to form the [Ni(tpfpp)] complex has been kinetically investigated using diaquabis(1,1,1,5,5,5-hexafluoropentane-2,4dionato)nickel(II), [Ni(hfac)2(H2O)2], in supercritical carbon dioxide (scCO2) medium in a spectrophotometric cell at various temperatures and pressures. The metalation reaction is first order with respect to porphyrin under the conditions where [Ni(hfac)2(H2O)2] is in a large excess relative to H2tpfpp. The saturation dependence was observed for the conditional first-order rate constants as a function of the mole fraction (XNi) of the excess [Ni(hfac)2(H2O)2]. Such dependence suggests that the metalation reaction consists of a fast pre-equilibrium of the formation of the outer-sphere association between [Ni(hfac)2(H2O)2] and H2tpfpp and a first-order rate-determining nickel(II) ion incorporation into the porphyrin core. The conditional first-order rate constants kobs are well expressed by kobs = KkxNi/(1 + KXNi), where K is the equilibrium constant for the formation of the outer-sphere association and k is the first-order rate constant for the nickel(II) ion incorporation. The thermodynamic and kinetic parameters are obtained as follows: ΔH° = 14.4 ± 1.3 kJ mol-1 at 20.5 MPa, ΔAS° = 133 ± 4 J mol-1 K-1 at 20.5 MPa and ΔV° = 15 ± 1 cm3 mol-1 at 333.3 K for the pre-equilibrium; ΔH≠ = 110 ± 5 kJ mol-1 at 20.5 MPa, ΔS≠ = 22 ± 16 J mol-1 K-1 at 20.5 MPa, and ΔV≠=81 ± 8 cm3 mol-1 at 333.3 K for the rate-determining step. The positive change in enthalpy and volume and significant positive change in entropy strongly indicate that the outer-sphere association is derived from the desolvation of reactants in scCO2.

Synthesis of non-aggregating chlorins and isobacteriochlorins from meso-tetrakis(pentafluorophenyl)porphyrin: A study using 1,3-dipolar cycloadditions under mild conditions

The 1,3-dipolar cycloaddition of meso-tetrakis(pentafluorophenyl)porphyrin and its nickel complex, with the bulky azomethine ylide dipole was studied under mild conditions, and yielded chlorin and isobacteriochlorin derivatives self-prevented from aggregation. The reactions were performed at room temperature or 0 C, and we were able to establish a set of reaction conditions to obtain only the chlorin or the isobacteriochlorin. These compounds were evaluated in solution, and no aggregation was observed at less than 25 mM (～30 mg mL-1) using 1H NMR experiments.

Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production

We employ facile aromatic nucleophilic substitution between the mercapto (-SH) and arylfluoro (Ar-F) groups to achieve extensive and robust cross-linking of a coordination host by porphyrin guests that also serve the purpose of versatile postsynthetic fun

Fluorinated maleimide-substituted porphyrins and chlorins: Synthesis and characterization

Maleimide-containing fluorinated porphyrins and chlorins were prepared based on the reaction of Zn(II) or Ni(II) complexes of 5,10,15,20-tetrakis(4-amino-2,3,5,6-tetrafluorophenyl)porphyrin and chlorin with maleic anhydride. Porphyrin maleimide derivative

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.

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.

One-Pot Approach to Chlorins, Isobacteriochlorins, Bacteriochlorins, and Pyrrocorphins

A Diels-Alder strategy is reported to synthesize the complete set of hydroporphyrins: chlorins, bacteriochlorins, isobacteriochlorins, and pyrrocorphins. Porphyrins and Ni-porphyrins react with isobenzofuran in very high yields at 70 °C to form the corres

Enhancing the reactivity of nickel(II) in hydrogen evolution reactions (HERs) by β-hydrogenation of porphyrinoid ligands

Fine-tuning of the porphyrin β-periphery is important for naturally occurring metal tetrapyrroles to exert diverse biological roles. Here we describe how this approach is also applied to design molecular catalysts, as exemplified by Ni(ii) porphyrinoids catalyzing the hydrogen evolution reaction (HER). We found that β-hydrogenation of porphyrin remarkably enhances the electrocatalytic HER reactivity (turnover frequencies of 6287 vs. 265 s-1 for Ni(ii) chlorin (Ni-2) and porphyrin (Ni-1), and of 1737 vs. 342 s-1 for Ni(ii) hydroporpholactone (Ni-4) and porpholactone (Ni-3), respectively) using trifluoroacetic acid (TFA) as the proton source. DFT calculations suggested that after two-electron reduction, β-hydrogenation renders more electron density located on the Ni center and thus prefers to generate a highly reactive nickel hydride intermediate. To demonstrate this, decamethylcobaltocene Co(Cp?)2 was used as a chemical reductant. [Ni-2]2- reacts ca. 30 times faster than [Ni-1]2- with TFA, which is in line with the electrocatalysis and computational results. Thus, such subtle structural changes inducing the distinctive reactivity of Ni(ii) not only test the fundamental understanding of natural Ni tetrapyrroles but also provide a valuable clue to design metal porphyrinoid catalysts.

Coordination-Induced Spin-State-Switch (CISSS) in water

We present a non-ionic water-soluble porphyrin that does not exhibit measurable aggregation even at high concentrations in water. The spin state of the corresponding nickel(ii) complex changes from completely diamagnetic (low-spin) to paramagnetic (high-s