98716-00-8

Upstream product

• 80937-33-3 oxygen 
• 99038-25-2 [meso-5,10,15,20-tetrakis-(2,6-difluorophenyl)porhpyrinato]-iron(III) chloride 
• 4217-54-3 9,10-dihydro-10-methylacridine 
• 92-83-1 xanthene 
• 162257-76-3 tetrakis(2,6-difluorophenyl)porphyrinate^(2-)iron(II) 
• 96-76-4 2,4-di-tert-Butylphenol 
• 379217-58-0 superoxo(tetrakis(2,6-difluorophenyl)porphyrinato)(tetrahydrofuran)iron(III) 
• 1206795-61-0 C₄₄H₂₀F₈FeN₄⁽¹⁺⁾*F₆Sb^(1-) 
• 7732-18-5 water 

Downstream Products

• 180151-16-0 perchloratoiron(III) tetrakis(2,6-difluorophenylporphyrin) 
• 162257-76-3 tetrakis(2,6-difluorophenyl)porphyrinate^(2-)iron(II) 

Relevant academic research and scientific papers

A selective stepwise heme oxygenase model system: An iron(IV)-oxo porphyrin π-cation radical leads to a verdoheme-type compound via an isoporphyrin intermediate

The selective oxidation of the α-position of two heme-Fe III tetraarylporphryinate complexes occurs when water(hydroxide) attacks their oxidized Cmpd I-type equivalents, high-valent FeIV=O π-cation radical species ((P+?)FeIV=O). Stepwise intermediate formation occurs, as detected by UV-vis spectroscopic monitoring or mass spectrometric interrogation, being iron(III) isoporphyrins, iron(III) benzoyl-biliverdins, and the final verdoheme-like products. Heme oxygenase (HO) enzymes could proceed through heterolytic cleavage of an iron(III)-hydroperoxo intermediate to form a transient Cmpd I-type species.

Heme/O2/?NO nitric oxide dioxygenase (NOD) reactivity: Phenolic nitration via a putative heme-peroxynitrite intermediate

(Chemical Equation Presented) An oxy-heme complex, the heme-superoxo species (tetrahydrofuran)(F8)FeIII-(O2 ?-) (2) (F8 = an ortho-difluoro substituted tetraarylporphyrinate), reacts with nitrogen monoxide (?NO; nitric oxide) to produce a nitrato-iron(III) compound (F8)FeIII-(NO 3-) (3) (X-ray). The chemistry mimics the action of ?NO Dioxygenases (NODs), microbial and mammalian heme proteins which facilitate ?NO detoxification/homeostasis. A peroxynitrite intermediate complex is implicated; if 2,4-di-tert-butylphenol is added prior to ?NO reaction with 2, o-nitration occurs giving 2,4-di-tert-butyl-6-nitrophenol. The iron product is (F8)FeIII-(OH) (4). The results suggest that heme/O2/?NO chemistry may lead to peroxynitrite leakage and/or exogenous substrate oxidative/nitrative reactivity.

Hydrogen atom abstraction and hydride transfer reactions by iron(IV)-oxo porphyrins

(Chemical Equation Presented) True identity revealed: The C-H bond activation of alkyl aromatics by synthetic iron(IV)-oxo porphyrin species and the hydride transfer of NADH analogues to them occur through H-atom abstraction and proton-coupled electron-transfer mechanisms, respectively. Mechanistic studies revealed that iron(IV)-oxo porphyrin π, not iron(IV)-oxo porphyrin pradical cations, are the true oxidant.

Generation and characterization of [(P)M-(X)-CO(TMPA)]n+ assemblies; P = porphyrinate, M = FeIII and CoIII, X = O2-, OH-, O22-, and TMPA = tris(2-pyridylmethyl)amine

With the established chemistry of bridged [(porphyrinate)Fe III-X-CuII(ligand)]n+ [X = O2- (oxo), OH- (hydroxo), O22- (peroxo)] complexes, we investigated the effect of cobalt ion substitution for copper or copper and iron. Thus, in this report, the generation and characterization of new μ-oxo, μ-hydroxo, and μ-peroxo (μ-X) assemblies of [(porphyrinate)M III-X-CoII/III(TMPA)]n+- assemblies is described, where M = FeIII or CoIII and TMPA = tris(2-pyridylmethyl)amine. The μ-oxo complex [(F8TPP)Fe III-O-CoII(TMPA)]+ (1, F8TPP = tetrakis(2,6-difluorphenyl)-porphyrinate) was isolated by an acid-base self-assembly reaction of a 1:1 mixture of (F8TPP)FeIII-OH and [CoII(TMPA)(MeCN)]2+ upon addition of triethylamine. The crystal structure of 1·2C4H10O proved the presence of an unsupported Fe-O-Co moiety; ∠Fe-O-Co = 171.6° and d(Fe...Co) = 3.58 A. Complex 1 was further characterized by UV-vis (λmax = 437 (Soret) and 557 nm), 1H NMR [δ 40.6 (pyrrole-H), 8.8 and 8.7 (m-phenyl-H), 8.0 (p-phenyl-H), 4.4 (PY-4H), 2.6 (PY-3H), 1.0 (PY-5H), -1.1 (PY-6H), and -2.7 (TMPA-CH2-) ppm], electrospray ionization (ESI) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometric methods, Evans method NMR (μeff = 3.1), and superconducting quantum interference device (SQUID) susceptometry (J = -114 cm-1, S = 1). The μ-hydroxo analogue [(F8TPP)FeIII-(OH)-CoII(TMPA)] + (2) [UV-vis λmax = 567 nm; δ 78 ppm (pyrrole-H); Evans NMR μeff = 3.7] was generated by addition of 1 equiv of triflic acid to 1. The protonation is completely reversible, and 1 is regenerated from 2 by addition of triethylamine. While (F8TPP)Fe II/[CoII(TMPA)(MeCN)]2+/O2 chemistry does not lead to a stable μ-peroxo species, a dicobalt μ-peroxo complex [(TPP)CoIII(O22-)-CoIII(TMPA)] 2+ (3, TPP = meso-tetraphenylporphyrinate) forms from a reaction of O2 with a 1:1 mixture of the CoII precursor components at -80°C [UV-vis λmax = 435 (Soret), 548, and 583 (weak) nm; silent EPR spectrum; diamagnetic NMR spectrum]. The oxygenation/deoxygenation equilibrium is reversible; warming solutions of 3 releases ～1 equiv of O2 and the reduced complexes are reformed.

Copper-Dioxygen Reactivity Involved in the Formation of μ-oxoIII-O-CuIIL>+ Heterodinuclear Complexes (por = porphyrinate, L = tetradentate ligand), and Novel Synthesis of Square-Planar FeII(por) Species

In the reaction of FeII(por) species with I(MeCN)>+ and O2 to give μ-oxoIII-O-CuIIL>+ 3 (por = porphyrinate, L = tetradentate ligand), copper-dioxygen adducts or their decomposition products must be present, otherwise III-OH> or III-O-FeIII(por)> products appear; a novel synthesis of square-planar FeII(por) is also described.

X-ray structure and physical properties of the oxo-bridged complex [(F8-TPP)Fe-O-Cu(TMPA)]+, F8-TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2-), TMPA = tris(2-pyridylmethyl)amine: Modeling the cytochrome c oxidase Fe-Cu heterodinu

The iron/copper heterodinuclear center in cytochrome c oxidases has attracted the interest of inorganic chemists since this is the site of dioxygen (O2) four-electron four-proton reduction to water by the reduced enzyme, while the oxidized ("re

Solution spectroscopic studies of electrolytically generated iron(III) and iron(IV) tetrakis(2,6-difluorophenyl)porphyrin π cation radicals

Electrochemical oxidation of tetrakis(2,6-difluorophenylporphinato)haloiron(III) ([(F8-TPP)FeIIIX], where X = Cl- or F-) at high potentials in dichloromethane or nitromethane solution results in the generation of iron porphyrin radicals sufficiently stable for spectral characterization at ambient temperature. Proton, deuterium, and fluorine-19 NMR spectroscopic characterization has permitted evaluation of the oxidation state of the metal. Bulk electrolysis at a potential slightly anodic of the first oxidation wave (+1.45 V vs SCE) yields high-spin iron(III) (fluorophenyl)porphyrin radicals that exhibit unique NMR spectral properties in comparison with the nonfluorinated derivatives. Large alternate downfield and upfield phenyl proton and fluorine-19 NMR shifts point to formation of the porphyrin π cation radical with large unpaired spin density at the phenyl ortho fluorine position. Bulk electrolysis of [(F8-TPP)FeIIIX] at higher potentials (+1.60 V) results in the generation of an additional product presumably due to the removal of the second electron from the metal center. The NMR spectra of this unstable oxidized product are consistent with an iron(IV) porphyrin π-cation-radical species. Phenyl proton and fluorine signals are drastically shifted in directions opposite to those of the singly oxidized species. Evidence is thus presented for generation of the first iron(IV) porphyrin π-cation-radical species without an axial oxo ligand. Electrochemical oxidation of the dinuclear (μ-oxo)iron(III) porphyrin, [((pyrr-d8)-F8-TPP)Fe]2O at potentials of +1.20 and +1.50 V yields respective monocation and dication iron(III) porphyrin radical complexes.