Iron Dinitrogen Complexes Supported by Tris(NHC)borate Ligand: Synthesis, Characterization, and Reactivity Study

Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex

“…Reaction of the previously reported high-spin ( S = 3/2) iron(I) dinitrogen complex PhB(AdIm) 3 Fe-N 2 ( 1 ) 17 with equimolar N -methylmorpholine N -oxide (or pyridine- N -oxide) provides the purple iron(III) oxo complex PhB(AdIm) 3 Fe=O ( 2 ) in moderate isolated yield ( Scheme 1 ). The molecular structure of 2 has been determined by single-crystal X-ray diffraction, revealing a trigonally symmetric ( C 3 v symmetry) complex in which the iron oxo linkage lies on the molecular 3-fold axis (B–Fe–O angle = 178.15(9)°) ( Figure 1 a).…”

“…Similar transformations are catalyzed by certain nonheme iron(II) and 2-oxogluteratedependent oxygenases, including in DNA alkylation repair and antibiotic biosynthesis, albeit with the more highly oxidized [Fe IV O] 2+ intermediate. 15,16 Reaction of the previously reported high-spin (S = 3/2) iron(I) dinitrogen complex PhB(AdIm) 3 Fe-N 2 (1) 17 with equimolar N-methylmorpholine N-oxide (or pyridine-N-oxide) provides the purple iron(III) oxo complex PhB(AdIm) 3 FeO (2) in moderate isolated yield (Scheme 1). The molecular structure of 2 has been determined by single-crystal X-ray diffraction, revealing a trigonally symmetric (C 3v symmetry) complex in which the iron oxo linkage lies on the molecular 3fold axis (B−Fe−O angle = 178.15(9)°) (Figure 1a).…”

Nickel(II)-Methyl Complexes Adopting Idealized Seesaw Geometries

“…Solvents were dried on a solvent purification system from Pure Process Technologies and passed through a column of activated alumina before storing over 4 Å molecular sieves under N2. Diethyl ether and tetrahydrofuran (THF) were stirred over NaK alloy and passed through a column of activated alumina prior to storing over 4 [1][2][3][4] UV-vis spectra were recorded on a Thermo Scientific Evolution 300 spectrometer with the VISIONpro software suite. IR spectra were recorded on a Bruker Tensor II spectrometer with the OPUS software suite.…”

“…Nickel-alkyl complexes have been invoked as important intermediates in a host of chemical transformations including the production of acetic acid and cross-coupling reactions. [1][2][3][4][5][6] In all reported examples of crystallographically characterized Ni(II)-methyl complexes, a diamagnetic, square planar geometry is observed. 7,8 Despite this, catalytically active Ni(II)alkyl species may likely exhibit or transition through different coordination geometries.…”

Ammonia and Hydrazine from Coordinated Dinitrogen by Complexes of Iron(0)

“…In particular, iron‐containing catalysts are of interest given that iron is present in both the Haber–Bosch catalyst and in the enzyme nitrogenase utilized by most biological systems . Recent research by Peters, Nishibayashi, Mézailles, Shi and Deng in this area have demonstrated iron‐mediated catalysis on a laboratory scale.…”