Synthesis and characterization of trigonal bipyramidal FeIII complexes and their solution behavior.
Synthesis and characterization of trigonal bipyramidal FeIII complexes and their solution behavior.
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三角双锥体 FeIII 配合物的合成、表征及其溶液行为。
DOI：
10.1016/j.poly.2021.115384
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发表时间：
2021
期刊：
影响因子：
2.6
通讯作者：
Lee,Wei-Tsung
中科院分区：
文献类型：
--
作者：
Lugosan,Adriana;Todtz,SophiR;Alcázar,Andrew;Zeller,Matthias;Devery3rd,JamesJ;Lee,Wei-Tsung
合成了一系列由氧化还原非无辜NNN钳形配体CztBu（PyrR）2−（R =iPr，Me，or H）支撑的空气稳定的三角双锥FeIII配合物，对其进行了充分表征，并用于丙酮与FeIII中心之间相互作用的研究.从顺磁性1H NMR谱结合EPR和穆斯堡尔谱确定的磁矩表明存在一个高自旋铁中心。循环伏安法研究的特征在于两个准可逆事件，对应于金属中心的Fe III/II还原约-0.40 V（vs. Fc）和配体中心的CztBu（PyrR）2/CztBu（PyrR）2自由基点+氧化，电位接近+0.70 V（vs. Fc）。CH 2Cl 2中的紫外可见光谱显示了配体-金属电荷转移（LMCT）带，以及丙酮与CztBu（PyrH）2FeCl 2的配位。CztBu（PyrR）2FeCl 2的原位红外光谱和溶液电导率（η κ）的测量结果表明，丙酮与铁中心的缔合作用较弱.
A series of air-stable trigonal bipyramidal FeIIIcomplexes supported by a redox non-innocent NNN pincer ligand, CztBu(PyrR)2−(R =iPr, Me, or H), were synthesized, fully characterized, and utilized for the investigation of the interaction between acetone and the FeIIIcenter. The magnetic moments determined from the paramagnetic1H NMR spectra in conjunction with EPR and Mössbauer spectroscopy indicate the presence of a high-spin ferric center. Cyclic voltammetry studies feature two quasi-reversible events corresponding to a metal-centered FeIII/IIreduction around −0.40 V (vs. Fc) and a ligand-centered CztBu(PyrR)2/CztBu(PyrR)2radical dot+oxidation at potentials near +0.70 V (vs. Fc). UV–Visible spectroscopy in CH2Cl2showcases ligand–metal charge transfer (LMCT) bands, as well as coordination of acetone to CztBu(PyrH)2FeCl2. In situ IR spectroscopy and solution conductivity (̺κ) measurements of CztBu(PyrR)2FeCl2with varied equivalents of acetone reveal that acetone is weakly associated with the iron center.