The preparation of bis(pyrazolyl)cyclopentadienyl iron complexes is described. Isopropyl substitution promotes solubility of the iron chloride complex that serves as a precursor to several derivatives through ligand exchange. Modification of the cyclopentadienyl substituent to replace a pyrazolyl unit with a phenyl group favors formation of a substituted ferrocene complex.
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http://dx.doi.org/10.1039/d2dt00199c | DOI Listing |
Chem 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
RWTH Aachen University: Rheinisch-Westfalische Technische Hochschule Aachen, Institute of Inorganic Chemistry, 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, (NH4)2Fe(SO4)2*6H2O and [Fe(pic)3]Cl2*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.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India.
In our effort to establish a direct synthetic approach for bis(dihydridoborate) complexes of first-row transition metals, we have investigated the reactivity of [Cp*Fe(dppe)Cl] (dppe =1,2-bis(diphenylphosphino)ethane) with Na[BHL] (L =2-mercaptopyridine (mp) and 2-mercaptobenzothiazole (mbz)) that led to the formation of iron(II) dihydridoborate complexes, [Cp*Fe{κ-S,H,H-(HBH(L))}] 1 a-b (L=mp (1 a) and L=mbz (1 b)). Further, in an attempt to isolate the bis(dihydridoborate) complex of iron by the insertion of borane into the κ-N,S-chelated iron complex, [(dppe)Fe{κ-N,S-(mp)}] (2), we have isolated and structurally characterized a rare example of dimeric iron bis(dihydridoborate) complex, [Fe{κ-S,H,H-(HBH(mp))}], ΛΔ/ΔΛ-3 as pair of enantiomers. Interestingly, these enantiomers ΛΔ/ΔΛ-3 have two trans-[Fe{κ-S,H,H-(HBH(mp))}] moieties bridged through sulfur atoms of 2-mercaptopyridinyl ligands, where the iron centres are hepta-coordinated.
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