39393-88-9

Basic information

• Product Name: μ-oxo-bis[(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)]
• Synonyms: μ-oxo-bis[(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)]
• CAS NO: 39393-88-9
• Molecular Weight: 1193.24
• Mol File: 39393-88-9.mol

Chemical Properties

• CAS DataBase Reference: μ-oxo-bis[(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)](CAS DataBase Reference)
• NIST Chemistry Reference: μ-oxo-bis[(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)](39393-88-9)
• EPA Substance Registry System: μ-oxo-bis[(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)](39393-88-9)

Safety Data

• Hazardous Substances Data: 39393-88-9(Hazardous Substances Data)

Upstream product

• 28755-93-3 iron(III)octaethylporphyrin chloride 
• 83614-06-6 (2,3,7,8,12,13,17,18-tetraethylporphyrinato)Fe(III)(C₆H₅) 
• 1310-73-2 sodium hydroxide 

Downstream Products

• 54967-69-0 [Fe(III)(octaethylporphyrinato)(SPh)] 
• 206429-07-4 (2,4,6-trimethylthiophenolato)(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III) 
• 183674-78-4 [Fe(III)(octaethylporphyrinato)(S-2-CH₃CONHC₆H₄)] 
• 183674-79-5 [Fe(III)(octaethylporphyrinato)(S-2-t-BuCONHC₆H₄)] 
• 206429-08-5 [Fe(III)(octaethylporphyrinato)(S-4-CF₃CONHC₆H₄)] 
• 183674-77-3 [Fe(III)(octaethylporphyrinato)(S-2-CF₃CONHC₆H₄)] 
• 206429-06-3 [Fe(III)(octaethylporphyrinato)(S-2-CH₃C₆H₄)] 
• 837370-60-2 [Fe(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinato)(2-trifluoroacetylaminophenolato)] 
• 837370-59-9 [Fe(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinato)(2,6-bis(trifluoroacetylamino)phenolato)] 
• 1260435-32-2 Fe(III)(OEP)(sal) 
• 54967-69-0 (thiophenolato)(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III) 
• 1260435-30-0 Fe(III)(OEP)(4-tBu-Hcat) 

Relevant articles and documents

BIS-PHENANTHROLINE IRON MACROCYCLE COMPLEX FOR OXYGEN REDUCTION REACTION

Disclosed are compounds, compositions, and methods useful for the oxygen reduction reaction (ORR) and capable of operating efficiently at low overpotentials.

Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

The reaction of nitrite with ferric and ferrous porphyrins was examined using visible, infrared and NMR spectroscopy. Solutions of either ferric or ferrous porphyrin were stable in the presence of nitrite, with only complexation reactions being observed. Under voltammetric conditions, though, a rapid reaction between nitrite and iron porphyrins was observed to form the nitrosyl complex, Fe(P)(NO), where P=porphyrin. The products of the reduction of ferric porphyrins in the presence of nitrite were confirmed by visible spectroelectrochemistry to be Fe(P)(NO) and [Fe(P)]2O. Visible, NMR and infrared spectroscopy were used to rule out the formation of Fe(P)(NO) by the iron-catalyzed disproportionation of nitrite. A reaction between iron porphyrins and nitrite only occurred by the presence of both oxidation states (ferric/ferrous). The kinetics of the reaction were monitored by visible spectroscopy, and the reaction was found to be first-order with respect to Fe(OEP)(Cl) and Fe(OEP). The products were the same as those observed in the spectroelectrochemical experiment. The rate was not strongly dependent upon the concentration of nitrite, indicating that the coordinated, not the free nitrite, was the reaction species. The kinetics observed were consistent with a mixed oxidation state nitrite-bridged intermediate, which carried out the oxygen transfer reaction from nitrite to the iron porphyrin. The effect of nitrite coordination on the reaction rate was examined.

Electroreduction of μ-oxo iron(III) porphyrins adsorbed on an electrode leading to a cofacial geometry for the iron(II) complex: Unexpected active site for the catalytic reduction of O2 to H2O

Acidification of a solution of (μ-oxo)bis[(5,10,15,20- tetraphenylporphyrinato)iron(III)] ([{Fe(tpp)}2O], II) in CH2Cl2 produced equimolar amounts of a hydroxoiron(III) complex [(tpp)Fe(III)(OH)] (III) and an iron(III) complex [(tpp)Fe(III)(ClO4)] (IV). The complex IV was isolated as a perchlorate salt, which crystallized in the triclinic space group P1 (2); a = 11.909(3), b = 19.603(4), c = 10.494(3) A, α = 95.74(2)°, β = 107.91(2)°, γ = 89.14(2)°, V = 2319.1(9) A3, Z = 2, D(calc)= 1.328 g cm-3, μ(Mo Kα) = 4.35 cm-1, final R = 0.055 and R(w) = 0.050. The crystal structure of IV revealed that ClO4- is coordinated to the iron atom, which may be driven by the preference of iron(III) to be five coordinate rather than four coordinate. Reduction of the complex II in the presence of acid by electrolysis and/or by a reducing agent, such as sodium dithionite, under argon produced [Fe(II)(tpp)]. The addition of O2 to a solution of [Fe(tpp)] in acidic CH2Cl2 in the presence of an equimolar amount of the reducing agent produced the complex III. When the complex II was adsorbed on an electrode surface and placed in aqueous acidic electrolyte solutions, electroreduction of the adsorbate proceeded according to the half- reaction: [{Fe(tpp)}2O] +2H++2e-→2[Fe(tpp)]+H2O, at 0.031-0.059 pH V (vs. SCE, pH > 1.0). Based on these results, oxo-bridged iron(III) porphyrin dimers were used as electrocatalysts for the reduction of O2. The catalytic reduction of O2 proceeded at potentials in the vicinity of those for II. As a whole, the proportion of H2O as the product increased from 50% for adsorbed [(tpp)Fe(III)Cl] to > 90% for the adsorbed dimer. Thus, electroreduction of the dimer adsorbed on a carbon electrode immersed in aqueous acid produced two solid state, cofacially fixed iron(II) porphyrin molecules: [PFe(III)OFe(III)P](ad)+2H++2e-→[PFe(II) Fe(II)P](ad)+H2O (P = porphyrin dianion). Coordination of molecular oxygen to the adjacent two iron(II) centers under acidic conditions allowed formation of O2-bridged iron(III) porphyrin [PFe(III)(O2) Fe(III)P](ad) at the electrode surface. Electroreduction of the adsorbate under acidic conditions produced H2O and allowed the reformation of [PFe(II) Fe(II)P](ad). The implication is that the electroreduction of the adsorbed oxo-bridged dimer gives a cofacial geometry for PFe(II) on the electrode, facilitating the coordination and subsequent splitting of O2.

An unusual near-eclipsed porphyrin ring orientation in two crystalline forms of (μ-oxo)bis[(octaethylporphinato)iron(III)]. Structural and molecular mechanics studies

The structures of two polymorphs of (μ-oxo)bis[(octaethylporphinato)iron(III)], [Fe(OEP)]2O (C72H88Fe2N8O), have been determined by X-ray structure analyses using data collected with an area detector. The two [Fe(OEP)]2O polymorphs (a triclinic and a monoclinic form) show strong structural similarities. The eight Fe-Np bond distances have average values of 2.077(3) A? in the triclinic form and 2.080(5) A? in the monoclinic form. The average axial Fe-O bond lengths are 1.756(3) and 1.755(10) A? for the two structures, respectively. The average displacements of the iron(III) atom from the mean porphinato core are 0.50 A? in the triclinic form and 0.54 A? in the monoclinic form. The most important structural feature of the molecule in the two crystal forms is the near-eclipsed intramolecular porphyrin ring orientation: the average N-Fe-Fe′-N′ dihedral angles are 17.0(10)° in the triclinic form and 16.8(6)° in the monoclinic form. Molecular mechanics calculations have been carried out to explore the inter-ring orientation; these suggest that peripheral ethyl group interactions lead to the near-eclipsed orientation. Crystal data: triclinic form, a = 11.561(5) A?, b = 12.299(8) A?, c = 23.341(16) A?, α = 82.56(3)°, β = 81.94(7)°, γ = 79.18(1)°, space group P1, V = 3210(5) A?3, Z = 2, 8931 observed data, R1 = 0.050, R2 = 0.056; monoclinic form, a = 18.433(13) A?, b = 15.104(6) A?, c = 23.489(6) A?, β = 97.82(1)°, space group P21/c, V = 6479(9) A?3, Z = 4, 6169 observed data, R1 = 0.054, R2 = 0.060.

SYNTHESES AND MAGNETIC PROPERTIES OF ARYLIRON(III) COMPLEXES OF OCTAETHYLPORPHYRINS

Aryliron(III) octaethylporphyrins, OEP-FeIII(4-XC6H4) were obtained from octaethylporphyrinatoiron(III) perchlorate, OEP-FeIII(ClO4) and arylmagnesium bromides.In order to confirm the ESR parameters, the

Iron(II, III)-Chlorin and Isobacteriochlorin Complexes. Models of the Heme Prosthetic Groups in Nitrite and Sulfite Reductases: Means of Formation and Spectroscopoic and Redox Properties

Extensive series of iron(II, III)-hydroporphyrin complexes of the types Fe(P)L, 0,+, 2O, and Fe(P), with P = octaethylchlorin (OEC) and octaethylisobacteriochlorin (OEiBC) and L, L' = neutral or uninegative axial ligands, have been synthesized and isolated or generated in solution.Means of synthesis and reactivity properties of OEC and OEiBC complexes parallel those of octaethylporphyrin (OEP) complexes.This behavior, together with a detailed body of physicochemical properties (absorption, MCD, 1H NMR, EPR, and infrared spectra and voltammetry), serves to identity all new complexes.Certain of the OEiBC species are pertinent as possible analogues of the siroheme prosthetic group of nitrite and sulfite reductases.Physicochemical properties of OEP, OEC, and OEiBC complexes at parity of axial ligation are compared in an attempt to identify any intrinsic features of isobacteriochlorin species that might render them particularly suitable for mediation of multielectron reductions of substrates as executed by siroheme enzymes.Properties such as Fe(III)/Fe(II) potentials and νCO of Fe(P)L(CO) and Fe(P)(CO)1,2 were found to be nearly invariant to P, indicating little cis effect of these macrocycles, which are in different reduction levels.That property most dependent on macrocycle structure was found to be the potential for ring-based oxidation which increases in the order OEiBC OEC OEP.Comparative properties are discussed in some detail and are related to available information on sirohemes, including the question of axial ligation in the native enzyme.This research affords the first comprehensive examination of the preparation and chemical, spectroscopic, and redox properties of iron(II, III)-hydroporphyrin complexes.