The iron oxo unit, [Fe=O] is a critical intermediate in biological oxidation reactions. While its higher oxidation states are well studied, relatively little is known about the least-oxidized form [Fe=O]. Here, the thermally stable complex PhB(AdIm)Fe=O has been structurally, spectroscopically, and computationally characterized as a iron(III) oxo. An unusually short Fe-O bond length is consistent with iron-oxygen multiple bond character and is supported by electronic structure calculations. The complex is thermally stable yet is able to perform hydrocarbon oxidations, facilitating both C-O bond formation and dehydrogenation reactions.
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http://dx.doi.org/10.1021/acscentsci.1c00890 | DOI Listing |
Inorg Chem
January 2025
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States.
The nonheme iron(II) complexes containing a fluoride anion, Fe(BNPAO)(F) () and [Fe(BNPAOH)(F)(THF)](BF) (), were synthesized and structurally characterized. Addition of dioxygen to either or led to the formation of a fluoride-bridged, dinuclear iron(III) complex [Fe(BNPAO)(F)(μ-F)] (), which was characterized by single-crystal X-ray diffraction, H NMR, and elemental analysis. An iron(II)(iodide) complex, Fe(BNPAO)(I) (), was prepared and reacted with O to give the mononuclear complex -Fe(BNPAO)(OH)(I) ().
View Article and Find Full Text PDFActa Crystallogr C Struct Chem
December 2024
University of Melbourne, School of Chemistry, Grattan Street, Parkville, 3052, Australia.
Dalton Trans
November 2024
National Laboratory of Solid State Microstructures and Jiangsu Provincial Key Laboratory for Nanotechnology, College of Engineering and Applied Sciences, Nanjing University, Nanjing, Jiangsu 210093, People's Republic of China.
Chemistry
December 2024
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, Japan.
Decarboxylative alkylation of carboxylic acids with easily oxidizable functional groups such as phenol and indole functionalities was achieved using a catalytic amount of basic iron(III) acetate, Fe(OAc)(OH), in the presence of benzimidazole under 427 nm LED irradiation. Kinetic analyses of this catalytic reaction revealed that the reaction rate is first-order in alkenes and is linearly correlated with the light intensity; the faster reaction rate for the benzimidazole-ligated species was consistent with the increased absorbance in the visible light region. Wide functional group tolerance for the easily oxidizable groups is ascribed to the weak oxidation ability of the in situ-generated oxo-bridged iron clusters compared with other iron(III) species.
View Article and Find Full Text PDFChem
September 2023
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA.
Iron sulfur clusters are critical to a plethora of biological processes; however, little is known about the elementary unit of these clusters, namely the [Fe=S] fragment. Here, we report the synthesis and characterization of a terminal iron sulfido complex. Despite its high spin ( = 5/2) ground state, structural, spectroscopic, and computational characterization provide evidence for iron sulfur multiple bond character.
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