Hangman Fe(III) corroles catalyse H(2)O(2) disproportionation at a faster rate and display a more pronounced hangman effect than their one electron oxidized analogues owing to their ability to bypass high energy intermediates by redox-leveling derived from the use of the corrole as a non-innocent ligand.
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http://dx.doi.org/10.1039/c2cc30580a | DOI Listing |
Chemistry
January 2024
Schulich Faculty of Chemistry, Technion - Israel Institute of Technology Institution, Haifa, 32000, Israel.
Construction of functional synthetic systems that can reversibly bind and transport the most biologically important gaseous molecules, oxygen and nitric oxide (NO), remains a contemporary challenge. Myoglobin and nitrophorin perform these respective tasks employing a protein-embedded heme center where one axial iron site is occupied by a histidine residue and the other is available for small molecule ligation, structural features that are extremely difficult to mimic in protein-free environments. Indeed, the hitherto reported designs rely on sophisticated multistep syntheses for limiting access to one of the two axial coordination sites in small molecules.
View Article and Find Full Text PDFInorg Chem
December 2022
Schulich Faculty of Chemistry, Technion Institute of Technology, Haifa3200003, Israel.
Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [Htpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [Fetpfc(py)]COT and 6-coordinate [Fetpfc(py)]COT, with one and two axial pyridine ligands per metal, respectively.
View Article and Find Full Text PDFInorg Chem
December 2022
College of Materials Science and Optoelectronic Technology and Chinese Academy of Sciences Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Yanqi Lake, Huairou District, Beijing101408, P. R. China.
There have been debates on the electronic configurations of (nitrosyl)iron corroles for decades. In this work, pentacoordinate [Fe(TPC)(NO)], [Fe(TTC)(NO)], and [Fe(TFC)(NO)] with different -substituted phenyl groups (TPC, TTC, and TFC = tris(phenyl, 4-tolyl, or 4-fluorophenyl)corrole, respectively) have been isolated and investigated by various techniques including single-crystal X-ray diffraction, UV-vis spectroscopy, cyclic voltammetry, Fourier transform infrared, NMR, and absorption fine structure spectroscopy. Multitemperature and high-magnetic-field (3, 6, and 9 T) Mössbauer spectroscopy was also applied on all three complexes, which determined the = 0 diamagnetic states, consistent with the magnetic susceptibility and electron paramagnetic resonance measurements.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2022
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD, 21218, USA.
Inorg Chem
January 2020
Department of Biological, Physical, and Health Sciences , Roosevelt University, Chicago , Illinois 60605 , United States.
Metallocorroles wherein the metal ion is Mn and formally Fe are studied here using field- and frequency-domain electron paramagnetic resonance techniques. The Mn corrole, Mn(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole trianion), exhibits the following = 2 zero-field splitting (zfs) parameters: = -2.67(1) cm, || = 0.
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