Sterically Encumbered Coordination Sites. Iron(II) Complexes of Jäger-type ligands with a Terphenyl Backbone,Zeitschrift für anorganische und allgemeine Chemie

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Sterically Encumbered Coordination Sites. Iron(II) Complexes of Jäger-type ligands with a Terphenyl Backbone
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2021-07-19 , DOI: 10.1002/zaac.202100196
Andreas Dürrmann , Gerald Hörner ₁ , Stefan Wagner ₂ , Matthias Breuning ₂ , Birgit Weber ₃

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A Schiff base-like ligand H₂L^TerPh featuring a para-terphenyl backbone was synthesized and converted in two steps to an octahedral iron(II) coordination polymer with 1,2-bis-(4-pyridyl)-ethylene as bridging ligand. Single crystal X-ray structure analysis was possible for the free ligand and the two octahedral iron(II) complexes. The Schiff base-like ligand features a [N₂O₂]²⁻ coordination sphere for the metal center and the para-terphenyl backbone introduces intrinsic steric constraint. Characterization of the coordination polymer with an N₄O₂ coordination sphere around the iron center via magnetic measurements (SQUID) and room temperature Mössbauer spectroscopy revealed HS character in the entire temperature range investigated. Structure modelling with DFT calculations supports the findings, but support also the possibility of spin crossover in solution.

中文翻译：

空间阻碍的协调站点。Jäger 型配体与三联苯骨架的铁 (II) 配合物

合成了具有对三联苯骨架的类席夫碱配体H ₂ L ^TerPh并分两步将其转化为八面体铁 (II) 配位聚合物，其中 1,2-双-(4-吡啶基)-乙烯作为桥连配体。自由配体和两个八面体铁 (II) 配合物的单晶 X 射线结构分析是可能的。席夫碱样配体的金属中心具有 [ N ₂O ₂ ] ^2-配位球，对三联苯骨架引入了内在空间约束。用N ₄O ₂表征配位聚合物通过磁性测量 (SQUID) 和室温穆斯堡尔光谱分析铁中心周围的配位球，揭示了研究的整个温度范围内的 H2S 特征。使用 DFT 计算的结构建模支持这些发现，但也支持解决方案中自旋交叉的可能性。

更新日期：2021-07-19

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