Abstract
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: E1/2=0.15 V (1), E1/2=0.35 V (1 a), E1/2=0.44 V (1 b).
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