Structural Differences and Redox Properties of Unsymmetric Diiron PDIxCy Complexes,European Journal of Inorganic Chemistry

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Structural Differences and Redox Properties of Unsymmetric Diiron PDIxCy Complexes
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-01-30 , DOI: 10.1002/ejic.201901173
Andreas J. Hofmann ₁ , Christian Jandl ₁ , Corinna R. Hess ₁

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We present two bimetallic iron complexes, [Fe₂(PDIeCy)(OTf)₄] (1) and [Fe₂(PDIpCy)(THF)(OTf)₄] (2) coordinated by an unsymmetric ligand. The new ligand, PDIeCy (PDI = pyridyldiimine; e = ethyl; Cy = cyclam), is a variant of the previously reported PDIpCy (p = propyl) ligand, featuring a shorter linker between the two metal coordination sites. The structural and electronic properties of 1 and 2, both in the solid and solution state, were analyzed by means of X‐ray crystallography, and spectroscopic methods, including ¹⁹F‐NMR. The two ligand platforms yield markedly different diiron structures: the PDIeCy ligand permits formation of a bridged, µ‐OTf complex, while the two iron centers of the PDIpCy‐based 2 remain unconnected, directly, under all conditions examined. Both compounds contain electronically non‐coupled high‐spin (S = 2) ferrous centers, as established by Mössbauer spectroscopy and magnetic susceptibility studies. Cyclic voltammetry demonstrates the rich redox chemistry of the compounds, involving both ligand and metal‐centered redox processes. Moreover, we synthesized the two‐electron reduced [Fe₂(PDIeCy)]²⁺ form of 1, which contains the dianionic PDI^2– ligand, and represents a two‐electron charge localized complex.

中文翻译：

非对称Diiron PDIxCy配合物的结构差异和氧化还原特性

我们提出了两个双金属铁配合物[Fe ₂（PDIeCy）（OTf）₄ ]（1）和[Fe ₂（PDIpCy）（THF）（OTf）₄ ]（2）由不对称配体配位。新的配体PDIeCy（PDI =吡啶基二亚胺； e =乙基； Cy =环酰胺），是先前报道的PDIpCy（p =丙基）配体的变体，在两个金属配位点之间的连接子较短。通过X射线晶体学和光谱方法分析了1和2在固态和固溶态下的结构和电子性质，包括^19种核磁共振这两个配体平台产生的二价铁结构明显不同：PDIeCy配体允许形成桥接的µOTf络合物，而在所有检查的条件下，基于PDIpCy的2的两个铁中心直接保持不连接。根据穆斯堡尔光谱法和磁化率研究，这两种化合物都包含非电子耦合的高自旋（S = 2）铁中心。循环伏安法证明了化合物的丰富氧化还原化学作用，涉及配体和以金属为中心的氧化还原过程。此外，我们合成了两个电子还原的[Fe ₂（PDIeCy）] ²⁺的形式1，其中包含二价阴离子PDI ^2- 配体，代表了两个电子电荷的局部复合物。

更新日期：2020-01-31

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