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 - Funding Information:
This manuscript is dedicated to Dr. Eckhard Bill, friend, teacher, and spectroscopist extraordinaire. This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program, under Award DE-SC0006498. The authors thank Dr. Sangmin Kim (Princeton University) for helpful discussion.
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.
UR - http://www.scopus.com/inward/record.url?scp=85150411543&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85150411543&partnerID=8YFLogxK
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 -