Detection and characterization of the long-postulated iron-dioxygen-iron intermediate in the autoxidation of ferrous porphyrins

J, Chin Dh Del Gaudio; Gn, La Mar; Al, Balch

doi:10.1021/ja00458a046

Cited by 93 publications

(53 citation statements)

References 3 publications

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“…l-peroxo di-iron complexes have been frequently proposed as unstable intermediates. A first detection and characterization of a such intermediate was made in the autoxidation of ferrous porphyrins [17]. In a preliminary communication [5], we suggested 1h as intermediate in the decomposition of ferrocenium cations in polar organic solvents under oxygen.…”

Section: Oxidation Of Organic Substrates By Ferroceniumoxygen Adductsmentioning

confidence: 95%

Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: Decomposition, redox reactions and stabilization

Hurvois

Moinet

2005

Journal of Organometallic Chemistry

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Section: Oxidation Of Organic Substrates By Ferroceniumoxygen Adductsmentioning

confidence: 95%

Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: Decomposition, redox reactions and stabilization

Hurvois

Moinet

2005

Journal of Organometallic Chemistry

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“…106, No. 25, 1984 PFo" (2) In previous work, it has been possible to detect the first two intermediates in this path. Synthetic iron(I1) porphyrins, such as (meso-tetraphenylporphyrin)iron(II) (TPPFe") and (octaethylporphyrin)iron(II) (OEPFe") are oxygenated in an inert solvent (toluene or dichloromethane) at low temperatures to produce peroxo-bridged complexes PFe"'OOFe"'P.24 These can be observed by 'H N M R and electronic spectra and are stable in solution indefinitely at -70 OC.…”

Section: Methodsmentioning

confidence: 99%

Oxygenation patterns for iron(II) porphyrins. Peroxo and ferryl (FeIVO) intermediates detected by proton nuclear magnetic resonance spectroscopy during the oxygenation of (tetramesitylporphyrin)iron(II)

Balch¹,

Chan²,

Cheng³

et al. 1984

J. Am. Chem. Soc.

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154

110

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7779such as 2 are expected to be the most sensitive of aromatics to ring current effects, for normal biphenyl-type aromatics interaction between the rings will be more readily observed through UV spectra than nuclear magnetic resonance data. Experimental Section'H NMR spectra were determined in CDCI, on a Perkin-Elmer R32 (90 MHz) spectrometer and are reported in parts per million downfield from tetramethylsilane as internal standard. UV spectra were determined in cyclohexane on a Cary 17 spectrophotometer. Mass spectra were determined on a Hitachi Perkin-Elmer RMU-7 (high-resolution) or Finnigan 3300 (low-resolution) mass spectrometer at 70 eV. Microanalyses were performed by this department and by Canadian Microanalytical services Ltd. All evaporations were carried out under reduced pressure on a rotary evaporator at ca. 40 OC. Extracts were dried with anhydrous sodium sulfate.Bi(2,Z'-tmns -lob, 10c-dimethyl-lob, l0c-dihydropyrenyl) (2). A solution of n-butyllithium (0.2 mmol in hexane, 0.1 mL) was added under N, to a stirred solution of 2-bromo-~rans-10b,10c-dimethyl-1Ob,10c-dihydropyrene (5)e (50 mg, 0.16 mmol) in dry ether (2 mL) in a flamed flask. After 5 min this solution was added under N2 to a slurry of TlBr (0.08 g, 0.3 mmol) in benzene (2 mL) and ether (2 mL). The mixture was then heated under reflux with stirring for 4 h. It was then cooled, poured into water, and extracted with dichloromethane. The extract was washed, dried, and evaporated and the residue was chromatographed over silica gel. Pentane eluted first the green dimethyldihydropyrene 4, ca. 10 mg, and then the purple bipyrene 2, 13 mg (35% yield), as very dark greenish black crystals from methanol that formed purple solutions; mp ca. 195-199 OC dec; 'H NMR 8 9.46 (s, 4 H, H-1,3), 8.8-8.5 (m, 14 H, other ArH), -3.68 and -3.77 (s, 6 H each, CH,); MS, Mt. at m / e 462 402 (M -4CH3, 55) plus many doubly charged ions; UV A,, (log e,,,) 577 nm (4.20), 544 (sh, 4.13), 480 (sh, 3.80) 436 (3.83), 400 (4.12), 368 (4.72), 345 (4.42), 332 (sh, 4.35). Anal. Calcd for C,,H,,,: C, 93.46; H, 6.54; mol wt., 462.23. Found: C, 92.91; H, 6.06; mol wt, 462.24 (MS). When anhydrous CoC1, (0.8 g) was used as oxidant (reflux, 4 h) from bromide 5 (800 mg), there was obtained bipyrene 2 (1 50 mg, 25% yield), identical with the above sample. trans-10b,10c-Dimethyl-2-phenyl-lOb,lOc-dihydropyrene (3). A solution of phenyllithium (3.2 mmol in hexane 1.8 mL) was added to a (24%), 447 (M -CH,, 38), 432(M -2CH3, 26), 417 (M -3CH3 IOO),stirred slurry of CuBr (0.23 g 1.6 mmol) in dry ether (5 mL) at 0 OC under N,. After 30 min the solution was allowed to warm to ca. 20 OC and a solution of the bromodihydropyrene 58 (100 mg, 3.2 mmol) in dry ether (5 mL) was added. The mixture was kept at ca. 20 OC for 8 days. Nitrobenzene (0.2 mL) was then added and stirring maintained for ca. 15 min, after which the mixture was poured into water and extracted with dichloromethane. The extract was washed, dried, and evaporated, and the residue was chromatographed over silica gel using pentane...

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“…24). Reaction of two ferrous porphyrin subunits with O 2 re-forms the diiron(III)-m-oxo assembly via a Balch-type mechanism (164,165) for reentry into the oxidative process. In this way, a photocycle for organic substrate oxidation can be constructed using molecular oxygen as the terminal oxidant and oxygen atom source.…”

Section: B Photooxidation Chemistry Of Diiron(iii) L-oxo Pacman Archmentioning

confidence: 99%

Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers

Rosenthal¹,

Nocera²

2007

Progress in Inorganic Chemistry

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Detection and characterization of the long-postulated iron-dioxygen-iron intermediate in the autoxidation of ferrous porphyrins

Cited by 93 publications

References 3 publications

Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: Decomposition, redox reactions and stabilization

Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: Decomposition, redox reactions and stabilization

Oxygenation patterns for iron(II) porphyrins. Peroxo and ferryl (FeIVO) intermediates detected by proton nuclear magnetic resonance spectroscopy during the oxygenation of (tetramesitylporphyrin)iron(II)

Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers

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