Electronic Finetuning of a Bio-inspired Iron(II) tetra-NHC Complex by trans Axial Isocyanide Substitution.,Chemistry - An Asian Journal

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Electronic Finetuning of a Bio-inspired Iron(II) tetra-NHC Complex by trans Axial Isocyanide Substitution.
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2020-03-23 , DOI: 10.1002/asia.202000214
Jonas F Schlagintweit ₁ , Carolin Hintermeier ₁ , Markus R Anneser ₁ , Eva-Maria H J Esslinger ₁ , Stefan Haslinger ₁ , Fritz E Kühn ₁

Affiliation

The synthesis of trans axially substituted mono‐ (1 a ) and bis(tert ‐butylisocyanide) (1 b ) derivatives of the highly active homogeneous bio‐inspired iron(II) olefin epoxidation (pre‐)catalyst 1 bearing an equatorial macrocyclic tetra N ‐heterocyclic carbene and two trans axial labile acetonitrile ligands is reported. NMR spectroscopy and SC‐XRD indicate a considerable π‐backdonation from the iron(II) centres to the isocyanide ligand(s). The impact of isocyanide substitution on the electronic features of the complexes is studied by cyclic voltammetry revealing a significant increase in half‐cell potential assignable to the reversible Fe(II)/Fe(III) redox couple with an increasing number of isocyanides as a result of their π‐accepting properties: E_1/2=0.15 V (1 ), E_1/2=0.35 V (1 a ), E_1/2=0.44 V (1 b ).

中文翻译：

通过反轴异氰化物取代对仿生铁 (II) 四 NHC 复合物进行电子微调。

带有赤道大环四氮的高活性均相仿生铁(II)烯烃环氧化（预）催化剂1的反式轴向取代的单（ 1a ）和双（叔丁基异氰）（ 1b ）衍生物的合成报道了杂环卡宾和两个跨轴不稳定乙腈配体。 NMR 光谱和 SC-XRD 表明从铁 (II) 中心到异氰化物配体有相当大的 π 回馈。通过循环伏安法研究了异氰化物取代对配合物电子特征的影响，揭示了可逆 Fe(II)/Fe(III) 氧化还原电对的半电池电位显着增加，结果异氰化物数量增加它们的π接受性质：E _1/2 =0.15 V ( 1 )，E _1/2 =0.35 V ( 1 a )，E _1/2 =0.44 V ( 1 b )。

更新日期：2020-03-23

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