Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes through Primary and Secondary Coordination Sphere Modifications
Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes through Primary and Secondary Coordination Sphere Modifications
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DOI：
10.1021/acs.inorgchem.6b03071
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发表时间：
2017-05-01
影响因子：
4.6
通讯作者：
Fout, Alison R.
中科院分区：
文献类型：
--
作者：
Gordon, Zachary;Drummond, Michael J.;Fout, Alison R.
报道了亚氨基官能化的三（吡咯甲基）胺配体骨架N（xpi（R））（3）（L-X（R）; X = H，Br; R=环己基（Cy），苯基（Ph），2，6-二异丙基苯基（DIPP））的衍生化反应。模块化配体合成允许初级和次级配位球电子的容易修饰。合成了铁（II）-羟基配合物N（（X）pi（R））（（X）afa（R））（2）Fe（II）OH（（XLFeOH）-Fe-R-O-II），以确定配体修饰对配合物电子性质的影响，包括其化学和电化学氧化。循环伏安法表明，Fe（II/III）氧化还原对跨越400 mV的范围内的系列。转移电位的起源解释的基础上的铁（II）和铁（III）化合物的光谱，结构和理论分析。
The derivatization of the imino-functionalized tris-(pyrrolylmethyl)amine ligand framework, N(xpi(R))(3) (L-X(R); X = H, Br; R= cydohexyl (Cy), phenyl (Ph), 2,6- diisopropylphenyl (DIPP)), is reported. Modular ligand synthesis allows for facile modification of both the primary and secondary coordination sphere electronics. The iron (II)-hydroxo complexes, N ((X)pi(R)) ((X)afa(R))(2)Fe (II) OH ((XLFeOH)-Fe-R-O-II), are synthesized to establish the impact of the ligand modifications on the complexes' electronic properties, including their chemical and electrochemical oxidation. Cyclic voltammetry demonstrates that the Fe(II/III) redox couple spans a 400 mV range across the series. The origin of the shifted potential is explained based on spectroscopic, structural, and theoretical analyses of the iron(II) and iron(III) compounds.