TY - JOUR
T1 - Pentamethylcyclopentadienyl Metalloradical Iron Complexes Containing Redox Noninnocent α-Diimine-Type Ligands
T2 - Synthesis, Molecular, and Electronic Structures
AU - Park, Yoonsu
AU - Zhong, Hongyu
AU - Pabst, Tyler P.
AU - Kim, Junho
AU - Chirik, Paul J.
N1 - Publisher Copyright:
© 2023 American Chemical Society
PY - 2023/3/27
Y1 - 2023/3/27
N2 - The synthesis and characterization of pentamethylcyclopentadienyl iron complexes bearing the redox noninnocent α-diimine (N,N′-dimesitylbutane-2,3-diimine, MesDI) and α-iminopyridine (N-mesityl(pyridin-2-yl)ethanimine MesPI) ligands were explored. One-pot reduction and complexation of the cyclopentadienyl ring was accomplished by treatment of (κ2-N,N′)FeCl2 (N,N′= MesDI or MesPI) precursors with [C5Me5]Li. The resulting iron compounds were characterized by paramagnetic 1H NMR spectroscopy, magnetic susceptibility measurements, zero-field 57Fe Mössbauer spectroscopy, low-temperature electron paramagnetic resonance (EPR) spectroscopy, and cyclic voltammetry. The combined spectroscopic, structural, and density functional theory (DFT) computational data supported low-spin iron(III) compounds (SFe = 1/2) with π-acidic, formally doubly reduced chelating ligands.
AB - The synthesis and characterization of pentamethylcyclopentadienyl iron complexes bearing the redox noninnocent α-diimine (N,N′-dimesitylbutane-2,3-diimine, MesDI) and α-iminopyridine (N-mesityl(pyridin-2-yl)ethanimine MesPI) ligands were explored. One-pot reduction and complexation of the cyclopentadienyl ring was accomplished by treatment of (κ2-N,N′)FeCl2 (N,N′= MesDI or MesPI) precursors with [C5Me5]Li. The resulting iron compounds were characterized by paramagnetic 1H NMR spectroscopy, magnetic susceptibility measurements, zero-field 57Fe Mössbauer spectroscopy, low-temperature electron paramagnetic resonance (EPR) spectroscopy, and cyclic voltammetry. The combined spectroscopic, structural, and density functional theory (DFT) computational data supported low-spin iron(III) compounds (SFe = 1/2) with π-acidic, formally doubly reduced chelating ligands.
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U2 - 10.1021/acs.organomet.3c00027
DO - 10.1021/acs.organomet.3c00027
M3 - Article
AN - SCOPUS:85150411543
SN - 0276-7333
VL - 42
SP - 465
EP - 472
JO - Organometallics
JF - Organometallics
IS - 6
ER -