Chloro[5,10,15,20-tetrakis(pentafluorophenyl)porphinato]iron(III) 0.57-Toluene Solvate

Song, Bing; Swenson, Dale C.; Goff, Harold M.

doi:10.1107/s0108270198099259

Cited by 3 publications

(1 citation statement)

References 5 publications

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“…These three values do not indicate a correlation of D with the electron donating/withdrawing character in the porphyrin substituents (TMP, TPP, TPFPP). This is probably because the steric bulk of the aromatic substituents ensures they are near perpendicular to the porphyrin plane (crystal structures exist for the latter two), − thus hindering their conjugation with the π orbitals of the porphyrin. The more subtle electronegativity effect through the σ bonds likely explains the similarity of D and gives an indication of the magnitude of catalytic fine-tuning.…”

Section: Discussionmentioning

confidence: 99%

Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR

et al. 2019

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Ferric hangman porphyrins are bioinspired models for haem hydroperoxidase enzymes featuring an acid/base group in close vicinity to the metal center, which results in improved catalytic activity for reactions requiring O−O bond activation. These functional biomimics are examined herein with a combination of EPR techniques to determine the effects of the hanging group on the electronics of the ferric center. These results are compared to those for ferric octaethylporphyrin chloride [Fe(OEP)Cl], tetramesitylporphyrin chloride [Fe(TMP)Cl], and the pentafluorophenyl derivative [Fe(TPFPP)Cl], which were also examined herein to study the electronic effects of various substituents. Frequency-domain Fourier-transform THz-EPR combined with field domain EPR in a broad frequency range from 9.5 to 629 GHz allowed the determination of zero-field splitting parameters, revealing minor rhombicity E/D and D values in a narrow range of 6.24(8) to 6.85(5) cm −1 . Thus, the hangman porphyrins display D values in the expected range for ferric porphyrin chlorides, though D appears to be correlated with the Fe− Cl bond length. Extrapolating this trend to the ferric hangman porphyrin chlorides, for which no crystal structure has been reported, indicates a slightly elongated Fe−Cl bond length compared to the non-hangman equivalent.

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Section: Discussionmentioning

confidence: 99%

Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR

et al. 2019

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Oxo-Free Hydrocarbon Oxidation by an Iron(III)-Isoporphyrin Complex

et al. 2020

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Metal-halides that perform proton coupled electrontransfer (PCET) oxidation are an important new class of high-valent oxidant. In investigating metal-dihalides, we reacted [Fe III (Cl)(T-(OMe)PP)] (1, T(OMe)PP = meso-tetra(4-methoxyphenyl)porphyrinyl) with (dichloroiodo)benzene. An Fe III -meso-chloro-isoporphyrin complex [Fe III (Cl) 2 (T(OMe)PP-Cl)] (2) was obtained. 2 was characterized by electronic absorption, 1 H NMR, EPR, and X-ray absorption spectroscopies and mass spectrometry with support from computational analyses. 2 was reacted with a series of hydrocarbon substrates. The measured kinetic data exhibited a nonlinear behavior, whereby the oxidation followed a hydrogen-atom-transfer (HAT) PCET mechanism. The meso-chlorine atom was identified as the HAT agent. In one case, a halogenated product was identified by mass spectrometry. Our findings demonstrate that oxo-free hydrocarbon oxidation with heme systems is possible and show the potential for iron-dihalides in oxidative hydrocarbon halogenation.

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Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy

et al. 2010

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A systematic study of 12 ferric and ferrous Kbeta X-ray emission spectra (XES) is presented. The factors contributing to the Kbeta main line and the valence to core region of the spectra are experimentally assessed and quantitatively evaluated. While the Kbeta main line spectra are dominated by spin state contributions, the valence to core region is shown to have greater sensitivity to changes in the chemical environment. A density functional theory (DFT) based approach is used to calculate the experimental valence spectra and to evaluate the contributions to experimental intensities and energies. The spectra are found to be dominated by iron np to 1s electric dipole allowed transitions, with pronounced sensitivity to spin state, ligand identity, ligand ionization state, hybridization state, and metal-ligand bond lengths. These findings serve as an important calibration for future applications to iron active sites in biological and chemical catalysis. Potential applications to Compound II heme derivatives are highlighted.

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Chloro[5,10,15,20-tetrakis(pentafluorophenyl)porphinato]iron(III) 0.57-Toluene Solvate

Cited by 3 publications

References 5 publications

Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR

Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR

Oxo-Free Hydrocarbon Oxidation by an Iron(III)-Isoporphyrin Complex

Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy

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