Abstract

AbstractThe performance oftransaxially substituted mono‐(2 a) and bis(tert‐butylisocyanide) (2 b) complexes derived from the highly active bio‐inspired iron(II) (pre‐ )catalyst2containing an equatorial macrocyclic tetraN‐heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H2O2is used as oxidant in combination with the Lewis acid Sc(OTf)3as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π‐accepting isocyanide ligands does not improve the catalytic performance of2 aand2 bposed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.

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