Pentamethylcyclopentadienyl Metalloradical Iron Complexes Containing Redox Noninnocent ?-Diimine-Type Ligands: Synthesis, Molecular, and Electronic Structures

被引：2
|
作者：
Park, Yoonsu [1 ,2 ]
Zhong, Hongyu [1 ]
Pabst, Tyler P. [1 ]
Kim, Junho [1 ]
Chirik, Paul J. [1 ]
机构：
[1] Princeton Univ, Dept Chem, Frick Lab, Princeton, NJ 08544 USA
[2] Korea Adv Inst Sci & Technol KAIST, Daejeon 34141, South Korea
来源：
ORGANOMETALLICS | 2023年 / 42卷 / 06期
关键词：
CYCLOPENTADIENYLIRON DICARBONYL; HEME-PROTEINS; HYDROGENATION; THERMODYNAMICS; GENERATION; MECHANISM; CATALYSIS; OXIDATION; KINETICS; HYDRIDES;
D O I：
10.1021/acs.organomet.3c00027
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The synthesis and characterization of pentamethylcy-clopentadienyl iron complexes bearing the redox noninnocent alpha- diimine (N,N '-dimesitylbutane-2,3-diimine, MesDI) and alpha-iminopyr-idine (N-mesityl(pyridin-2-yl)ethanimine MesPI) ligands were explored. One-pot reduction and complexation of the cyclopentadienyl ring was accomplished by treatment of (kappa 2-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 Mo''ssbauer 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 pi-acidic, formally doubly reduced chelating ligands.
引用
收藏
页码：465 / 472
页数：8
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