Iron Porphyrin Complexes Research Articles

Synthesis, characterization, and reactivity of oxoiron(IV) porphyrin π-cation radical complexes bearing cationic N-methyl-2-pyridinium group

Electronic charge near the active site is an important factor for controlling the reactivity of metalloenzymes. Here, to investigate the effect of the cationic charge near the heme in heme proteins, we synthesized new iron porphyrin complexes (1 and 2) having cationic 3-methyl-N-methyl-2-pyrdinium group and N-methyl-2-pyridinium group at one of the four meso-positions, respectively. The N-methyl-2-pyridinium groups could be introduced by Stille coupling used palladium catalysts. Oxoiron(IV) porphyrin π-cation radical complexes (Compound I) of 1 (1-CompI) and 2 (2-CompI) are soluble in most organic solvents, allowing direct comparison of their electronic structure and reactivity with Compound I of tetramesitylporphyrin (3-CompI) and tetrakis-(2,6-dichlorophenyl)porphyrin (4-CompI) under the same conditions. Spectroscopic data for 1-CompI are close to those for 3-CompI, but the redox potential for 1-CompI is close to that of 4-CompI. Kinetic analysis of the epoxidation reactions shows that 1-CompI and 2-CompI are (~250-fold) more reactive than 3-CompI, and comparable to 4-CompI. DFT calculations allow to propose that the positive shift of the redox potential and the enhanced reactivity of 1-CompI and 2-CompI is induced by the intramolecular electric field effect of N-methyl-2-pyridinium cation, not by the electron-withdrawing effect.

Iron(III) Complexation with Galactodendritic Porphyrin Species and Hydrocarbons’ Oxidative Transformations

AbstractThe iron metalation of the known free‐base porphyrins H2P2 and H2P3, obtained by structural modification of the well‐known TPPF20 (H2P1) with galactose dendritic units, gave the corresponding iron(III) porphyrin complex FeP2 and the solid hybrid material FeP3S. Their synthesis, characterization and catalytic efficacy toward the oxidation of the organic substrates (Z)‐cyclooctene, cyclohexane and heptane, are reported. In this work, the possibility to modulate selectivity and chemical efficiency of the catalytic system by using simple and more sophisticated metalloporphyrins is demonstrated. Furthermore, the presence of the galactose dendrimer units at the meso‐porphyrin ring positions can tune the oxidation at the terminal positions in linear alkanes. In addition, the FeP3S material was easily recovered and reused at least 3 times for the cyclooctene oxidation. The catalytic performance of material FeP3S, associated with their possibility of reuse, makes this material a promising catalyst.

Repurposed and artificial heme enzymes for cyclopropanation reactions

Heme enzymes are some of the most versatile catalysts in nature. In recent years it has been found that they can also catalyze reactions for which there are no equivalents in nature. This development has been driven by the abiological catalytic reactivity reported for bio-inspired and biomimetic iron porphyrin complexes. This review focuss es on heme enzymes for catalysis of cyclopropanation reactions. The two most important approaches used to create enzymes for cyclopropanation are repurposing of heme enzymes and the various strategies used to improve these enzymes such as mutagenesis and heme replacement, and artificial heme enzymes. These strategies are introduced and compared. Moreover, lessons learned with regard to mechanism and design principles are discussed.

Carbon Dioxide Reduction: Modulation of Self‐Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO2 Reduction (Small 22/2021)

In article number 2006150, Mio Kondo, Shigeyuki Masaoka, and co-workers demonstrate that the self-assembly of iron porphyrin complexes with space modulators affords the porous crystalline solid with hydrophobic pores and adjacent active sites. The material efficiently catalyzes electrochemical CO2 reduction in aqueous media.

New insights on microscopic properties of metal-porphyrin complexes attached to quartz crystal sensor

A quartz crystal adsorbent coated with 5,10,15,20-tetrakis(4-methylphenyl) porphyrin was used to examine the complexation phenomenon of three metallic ions [aluminum(III), iron(III) and indium(III)]. The aim is to select the appropriate adsorbate for metalloporphyrin fabrication. The equilibrium adsorption isotherms of tetrakis(4-methylphenyl) porphyrin were performed at four temperatures (from 300 to 330 K) through the quartz crystal microbalance (QCM) method. Subsequently, the experimental data were analyzed in order to develop a thorough explanation of the complexation mechanisms. The experimental results indicated that the aluminum(III) chloride is the adequate material for metalloporphyrin application. Theoretical investigation was established through physics adsorption models in order to analyze the experimental isotherms. The AlCl3 isotherms were modeled via a single-layer adsorption model which is developed using the ideal gas law. Whereas, the FeCl3 isotherms were interpreted via a single-layer adsorption which includes the lateral interactions parameters (real gas law), indicating the lowest stability of the formed iron-porphyrin complex. The participation of the chloride ions in the double-layers adsorption of InCl3 was interpreted via layer by layer formulation. Interestingly, the physicochemical investigation of the three adopted models indicated that the tetrakis(4-methylphenyl) porphyrin adsorption was an endothermic process and that the aluminum(III) chloride can be recommended for an industrial application because it presents the highest adsorption energy (chemical bonds with porphyrins).

Homogeneous Electrocatalytic CO2Reduction Using a Porphyrin Complex with Flexible Triazole Units in the Second Coordination Sphere

The electrochemical reduction of carbon dioxide (CO2) to produce value-added chemicals is of great significance in mitigating environmental and energy concerns. In this work, an iron porphyrin catalyst, FePEG8T, with multiple triazole units tethered to a porphyrin ligand via flexible oxymethylene linkers, is reported for efficient electrocatalytic reduction of CO2 to afford carbon monoxide (CO). The electrocatalyst exhibits an excellent catalytic activity with a current density of −17.5 mA/cm2 and CO Faradaic efficiency of 95% at −2.5 V vs Fc/Fc+ in acetonitrile using water as the proton source. The maximum turnover frequency (TOFmax) was calculated to be 5.5 × 104 s–1 using foot-of-the-wave analysis, which is thirty times higher than the result from our previous zinc complex with the same triazole–porphyrin ligand. Control experiments on an iron porphyrin complex without triazole units confirm the contribution of triazole units on high catalytic activity. Long-term electrolysis of 40 h was also performed and demonstrated high catalyst stability. A normal KIE of 6.92 was obtained with H2O/D2O as the proton source at varying concentration ranges (0.5–5 M), suggesting that protonation of the catalyst–substrate intermediate is a rate-limiting step. Furthermore, the Tafel plot was generated for the catalyst FePEG8T for comparison with previously reported iron porphyrin catalysts. This work demonstrates an efficient CO2 reduction catalyst containing an iron metal center and a flexible triazole in the second coordination sphere toward CO formation with high stability, activity, and selectivity.

Effects of Appended Poly(ethylene glycol) on Electrochemical CO2 Reduction by an Iron Porphyrin Complex

Electrochemical carbon dioxide (CO2) reduction is a sustainable approach for transforming atmospheric CO2 into chemical feedstocks and fuels. To overcome the kinetic barriers of electrocatalytic CO2 reduction, catalysts with high selectivity, activity, and stability are needed. Here, we report an iron porphyrin complex, FePEGP, with a poly(ethylene glycol) unit in the second coordination sphere, as a highly selective and active electrocatalyst for the electrochemical reduction of CO2 to carbon monoxide (CO). Controlled-potential electrolysis using FePEGP showed a Faradaic efficiency of 98% and a current density of -7.8 mA/cm2 at -2.2 V versus Fc/Fc+ in acetonitrile using water as the proton source. The maximum turnover frequency was calculated to be 1.4 × 105 s-1 using foot-of-the-wave analysis. Distinct from most other catalysts, the kinetic isotope effect (KIE) study revealed that the protonation step of the Fe-CO2 adduct is not involved in the rate-limiting step. This model shows that the PEG unit as the secondary coordination sphere enhances the catalytic kinetics and thus is an effective design for electrocatalytic CO2 reduction.

Statistical Physics Modeling of Sorption Isotherms of Aluminum, Iron, and Indium on Tetraphenylporphyrin (H2TPP) and Tetrakis(4-tolylphenyl)porphyrin (H2TTPP): Phenomenological Investigation of Metalloporphyrins at the Molecular Level

A quartz crystal adsorbent functionalized with two promising porphyrins (the 5,10,15,20-tetrakis(4-tolylphenyl)porphyrin and the 5,10,15,20-tetraphenylporphyrin) was applied for the investigation of the adsorption phenomenon of aluminum chloride, iron chloride, and indium chloride. The aim is to prove new insights about the appropriate adsorption materials for metalloporphyrin fabrication. The equilibrium isotherms were measured at five adsorption temperatures (from 290 to 330 K) through the microbalance (QCM) method. The discussion of the experimental observations indicated that the adsorption of the aluminum chloride and the iron chloride was performed via a monolayer process. On contrary, the participation of the chloride ions in the double-layer adsorption of the indium chloride was explained by the layer-by-layer process. Overall, the statistical physics modeling of the experimental curves indicated that the number of ions per adsorbent site [Formula: see text] was found inferior to 1 for all the adsorption systems (multi-interaction process for the three ions). Interestingly, the physicochemical investigation of the three adopted models showed that the complexation mechanism of the tested porphyrins was an endothermic process since the two steric parameters ([Formula: see text] and [Formula: see text]) increased with the rise of the temperature. The FeCl3 curves were discussed via a monolayer adsorption model which includes the parameters [Formula: see text] and [Formula: see text] (lateral interaction description), indicating the lowest stability of the formed iron-porphyrin complex. The energetic study showed that the adsorption energies [Formula: see text] of AlCl3 on H2TTPP and H2TPP are superior to 40 kJ/mol (chemical adsorption mechanism), whereas the adsorption mechanisms of FeCl3 and InCl3 took place via a physical process since they presented adsorption energy values lower than 40 kJ/mol.

Iron-Catalyzed Highly para-Selective Difluoromethylation of Arenes.

Direct functionalization of a C-H bond at either the meta or para position by only changing the catalyst system poses a significant challenge. We herein report the [Fe(TPP)Cl]-enabled, selective, C-H difluoromethylation of arenes using BrCF2CO2Et as the difluoromethylation source, which successfully altered the selectivity from the meta to the para position. A preliminary mechanistic study revealed the iron porphyrin complex not only activated the aromatic ring but also induced para selectivity due to the influence of ligand sterics.

Nitric Oxide Dioxygenation by O2 Adducts of Manganese Porphyrins.

We describe here nitric oxide dioxygenation (NOD) by the dioxygen manganese porphyrin adducts Mn(Por)(η2-O2) (Por2- = the meso-tetra-phenyl or meso-tetra-p-tolylporphyrinato dianions, TPP2- and TTP2-). The Mn(Por)(η2-O2) was assembled by adding O2 to sublimed layers of MnII(Por). When NO was introduced and the temperature was slowly raised from 80 to 120 K, new IR bands with correlated intensities grew concomitant with depletion of the υ(O2) band. Isotope labeling experiments with 18O2, 15NO, and N18O combined with DFT calculations provide the basis for identifying the initial intermediates as the six-coordinate peroxynitrito complexes (ON)Mn(Por)(η1-OONO). Further warming to room temperature led to formation of the nitrato complexes Mn(Por)(η1-ONO2), thereby demonstrating the ability of these metal centers to promote NOD. However, comparable quantities of the nitrito complexes Mn(Por)(η1-ONO) are also formed. In contrast, when the analogous reactions were initiated with the weak σ-donor ligand tetrahydrofuran or dimethyl sulfide present in the layers, formation of Mn(Por)(η1-ONO2) is strongly favored (∼90%). The latter are formed via a 6-coordinate intermediate (L)Mn(Por)(η1-ONO2) (L = THF or DMS) that loses L upon warming. These reaction patterns are compared to those observed previously with analogous iron and cobalt porphyrin complexes.

Effect of Pendant Distal Residues on the Rate and Selectivity of Electrochemical Oxygen Reduction Reaction Catalyzed by Iron Porphyrin Complexes

Oxygen reduction reaction (ORR) is a complex 4e–/4H+ multistep process, and factors that determine the rate and selectivity of this reaction are a matter of contemporary interest. Synthetic iron po...

Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins.

The manipulation of the second coordination sphere for improving the electrocatalytic CO2 reduction has led to breakthroughs with hydrogen bonding, local proton source, or electrostatic effects. We have developed two atropisomers of an iron porphyrin complex with two urea functions acting as multiple hydrogen-bonding tweezers to lock the metal-bound CO2 in a similar fashion found in the carbon monoxide dehydrogenase (CODH) enzyme. The αα topological isomer with the two urea groups on the same side of the porphyrin provides a stronger binding affinity to tether the incoming CO2 in comparison to the αβ disposition. However, the electrocatalytic activity of the αβ atropisomer outperforms its congener with one of the highest reported turnover frequencies at low overpotential. The strong H/D kinetic isotope effect (KIE) observed for the αα system indicates the existence of a tight water hydrogen-bonding network for proton delivery which is disrupted by addition of an acid source. The small H/D KIE for the αβ isomer and the enhanced electrocatalytic performance on addition of stronger acid indicate the free access of protons to the bound CO2 on the opposite side of the urea arm.

Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins

AbstractThe manipulation of the second coordination sphere for improving the electrocatalytic CO2 reduction has led to breakthroughs with hydrogen bonding, local proton source, or electrostatic effects. We have developed two atropisomers of an iron porphyrin complex with two urea functions acting as multiple hydrogen‐bonding tweezers to lock the metal‐bound CO2 in a similar fashion found in the carbon monoxide dehydrogenase (CODH) enzyme. The αα topological isomer with the two urea groups on the same side of the porphyrin provides a stronger binding affinity to tether the incoming CO2 in comparison to the αβ disposition. However, the electrocatalytic activity of the αβ atropisomer outperforms its congener with one of the highest reported turnover frequencies at low overpotential. The strong H/D kinetic isotope effect (KIE) observed for the αα system indicates the existence of a tight water hydrogen‐bonding network for proton delivery which is disrupted by addition of an acid source. The small H/D KIE for the αβ isomer and the enhanced electrocatalytic performance on addition of stronger acid indicate the free access of protons to the bound CO2 on the opposite side of the urea arm.

N–H insertion reaction via an iron carbenoid from α-diazophenylpropionate and its application to the formal total synthesis of stizolobinic acid

Abstract The formal total synthesis of the non-proteinogenic amino acid stizolobinic acid was accomplished relying as key step on an iron carbenoid-based N–H insertion reaction. The N–H insertion of α-diazophenylpropionate and benzylamine derivative catalyzed by tetrakis(pentafluorophenyl)porphyrin iron (III) chloride afforded the desired N–H insertion product in 79% yield. This is the first example of an N–H insertion involving α-diazophenylpropionate and an aliphatic amine catalyzed by an iron(III) porphyrin complex.

Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture.

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (≈550 cm-1 ) of the intermediate-spin S=3/2 excited states to the high-spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin-admixture model evidences a sizable contribution (≈15 %) of S=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm-1 ). Frequency-domain EPR spectroscopy allowed the mS = |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero-field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field-domain EPR studies are consistent with this model, which is also supported by theoretical calculations.

The Simplest Iron μ-oxo Species. The Molecular Structure of {[Fe(porphine)]2O}

We have prepared a new [Formula: see text]-oxo iron(III) porphyrin complex based on the simplest possible porphyrin ligand, porphine. Our structure determination for {[Fe(porphine)]2O}shows that it has a decidedly different molecular structure compared to all other [Formula: see text]-oxo iron(III)porphyrin complexes with two independent porphyrin ligands. The Fe–O–Fe angle is 153.21 (16)[Formula: see text]which leads to a small interplanar angle of 22.7[Formula: see text]between the two porphine rings. This also leads to C[Formula: see text]C nonbonded contact as short as 3.35Å between the two rings. The twist angle of the two porphine rings is 16.8[Formula: see text]. Other structural features are in general accord with those expected for high-spin iron(III) porphyrinates.

Towards spin quantum materials: Structure and potential energy profiles of weakly interacting arrays of iron porphyrin complexes at graphene armchair nanoribbon

The atomic structure, the rates of atomic spin polarization and potential energy profiles of heterostructure composed by iron porphyrin deposited on armchair graphene nanoribbon (FeP/AGNR) were investigated using density functional theory (DFT). The multiplicity of the Fe+2 ion in iron porphyrin for all possible types of coordination was determined as a triplet. Two possible η2 and η6 types of FeP coordination on AGNR were located with 0.43 and 0.15 kcal/mol forward and reversed potential barriers and 39% and 61% Arrhenius populations, respectively. It was found that FeP/AGNR can be used for perspective spin quantum applications due to localized spin-flip transition in IR A spectral region.

Elucidating the effect of the ionic liquid type and alkyl chain length on the stability of ionic liquid-iron porphyrin complexes.

The present study is motivated by the long-term objective of understanding how ionic liquids are biodegraded by cytochrome P450, which contains iron porphyrin (FeP) serving as the catalytic center. To this end, the current study is designed to elucidate the impact of types and conformations of ionic liquids on the binding energy with FeP, the key interactions that stabilize the ionic liquid-FeP complex, and how the electron uptake ability of FeP is altered in the presence of ionic liquids. Four classes of ionic liquids are considered: 1-alkyl-3-methylimidazolium, 1-alkyl-pyridinium, 1-alkylsulfonium, and N-methyl-N-alkylpyrrolidinium. The influence of linear alkyl chains of ethyl, butyl, hexyl, octyl, and decyl is examined on the favorable binding modes with FeP, considering two widely different conformations: tail up and tail down with respect to FeP. Electronic structure calculations are performed at the M06 level of theory with the 6-31G(d,p) basis set for C, H, and N atoms, while the Lanl2DZ basis set is employed for Fe. Donor-acceptor interactions contributing to the binding of ionic liquids to FeP are unraveled through the natural bond orbital analysis. The results from this study indicate that the binding energies are dependent not only on the class of ionic liquids but also on the conformations presented to FeP. The propensity of FeP to acquire an electron is significantly enhanced in the presence of ionic liquid cations, irrespective of the type and the alkyl chain length.

Exact semi-classical light-matter interaction operator applied to two-photon processes with strong relativistic effects.

X-ray processes involve interactions with high-energy photons. For these short wavelengths, the perturbing field cannot be treated as constant, and there is a need to go beyond the electric-dipole approximation. The exact semi-classical light-matter interaction operator offers several advantages compared to the multipole expansion such as improved stability and ease of implementation. Here, the exact operator is used to model x-ray scattering in metal K pre-edges. This is a relativistic two-photon process where absorption is dominated by electric-dipole forbidden transitions. With the restricted active space state-interaction approach, spectra can be calculated even for the multiconfigurational wavefunctions including second-order perturbation. However, as the operator itself depends on the transition energy, the cost for evaluating integrals for hundreds of thousands unique transitions becomes a bottleneck. Here, this is solved by calculating the integrals in a molecular-orbital basis that only runs over the active space, combined with a grouping scheme where the operator is the same for close-lying transitions. This speeds up the calculations of single-photon processes and is critical for the modeling of two-photon scattering processes. The new scheme is used to model Kα resonant inelastic x-ray scattering of iron-porphyrin complexes with relevance to studies of heme enzymes, for which the total computational time is reduced by several orders of magnitude with an effect on transition intensities of 0.1% or less.

Harnessing Noninnocent Porphyrin Ligand to Circumvent Fe-Hydride Formation in the Selective Fe-Catalyzed CO2 Reduction in Aqueous Solution

The iron–porphyrin complex with four positively charged N,N,N-trimethyl-4-ammoniumphenyl substituents (called WSCAT) is an efficient catalyst for the reduction of CO2 to CO in aqueous solution with...