A dinuclear helical iron(ii) complex of a new ditopic thiazolylimine ligand (L) has been synthesised via supramolecular assembly. The resulting dinuclear helical cylinder [FeL]·4BF was investigated by variable temperature X-ray crystallography, ESI high resolution mass spectrometry, CHN analysis, FT-IR and UV-Vis spectroscopy. The nature of the spin transition was investigated by magnetic susceptibility measurements, and confirmed by VT-SCXRD and X-ray photoelectron spectroscopy. [FeL]·4BF displays a complete spin transition with a gradual-abrupt character at T = 348 K and represents a new example of a dinuclear iron(ii) complex exhibiting a spin transition at high temperature. Both VT-SCXRD and XPS measurements show excellent correlation with the magnetic susceptibility experiments, demonstrating the power of XPS not just to confirm, but also to clearly follow the spin-state transition in Fe(ii) SCO complexes.
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http://dx.doi.org/10.1039/c7dt04190j | DOI Listing |
R Soc Open Sci
January 2025
Department of Industrial Chemistry, College of Natural and Applied Sciences, Addis Ababa Science and Technology University, PO Box 16417, Addis Ababa, Ethiopia.
The asymmetric Schiff base prepared from ethylenediamine and pyridine-2-carboxaldehyde reacts with Fe(ClO)·6HO to form the Fe(II) complex [FeL](ClO) with L = ,-diethyl-'-(pyridin-2-yl)methylene)ethane-1,2-diamine, where the Fe(III) starting material has been unexpectedly reduced to Fe(II). This complex was characterized by elemental analysis, infrared spectra, single crystal and powder X-ray diffraction measurements, variable temperature DC magnetic measurement and room temperature Mössbauer spectroscopy. The asymmetric ligand L coordinates in a tridentate fashion through its pyridyl, azomethine and amino nitrogen atoms, generating a distorted octahedral geometry around the central metal ion.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 03760, Republic of Korea.
We report the synthesis and characterization of an iron(III)-hydroperoxo complex generated from salicylate-assisted dioxygen activation by a cation-liganded iron(II) complex. Spectroscopic and theoretical data revealed stabilization of the end-on hydroperoxo ligand, and mechanistic insights, including a "V-shaped" Hammett plot, were confirmed by conducting oxygen atom transfer and proton-coupled electron transfer reactions.
View Article and Find Full Text PDFInorg Chem
December 2024
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 PDFInorg Chem
December 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, Hong Kong 999077, China.
Anilido-oxazoline-ligated iron complexes, including bis(anilido-oxazolinate) iron(II), mononuclear iron(II) alkyl and aryloxide, as well as the dinuclear analogues, were synthesized, and their catalytic performance on ring-opening polymerization (ROP) has been studied. Transmetalation of FeCl(THF) with in situ-generated anilido-oxazolinate lithium afforded the bis(anilido-oxazolinate) iron complexes and . Half-sandwich anilido-oxazolinate iron trimethylsilylalkyl complexes and could be synthesized in good yields via taking pyridine as an L-type ligand.
View Article and Find Full Text PDFChemistry
December 2024
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1a, 52074, Aachen, Germany.
In this study, we present the first experimental determination of the spin state of transition metal complexes by using Hirshfeld Atom Refinement. For the demonstration, the two iron(II) complexes, (NH)Fe(SO) ⋅ 6 HO and lFe(pic)jCl ⋅ EtOH were investigated. The method involves the refinement using wavefunctions of different spin multiplicity and comparison against experimental diffraction data by means of refinement indicators and residual electron density.
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