A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation

Abstract

The distinct oxidative reactivities reported here for the TMC-anti and TMC-syn isomers are surprising and require the examination of what factors can give rise to such differences for this class of iron complexes. In particular, our observation that the oxygen atom transfer reactivity of a nonheme FeIV=O unit can be so significantly enhanced by a simple flip in its orientation relative to its macrocyclic tetraamine host is truly remarkable and suggests that there is much more that can be learned for catalyst design by paying attention to the effect of ligand topology on the iron active site