Neighbouring effects on catalytic epoxidation by Fe-cyclam in M2-PDIxCy complexes

Abstract

The unsymmetric PDIeCy ligand, featuring pyridinediimine and cylam sites, can be selectively metalated. Complementing the diiron compound, we have synthesized two heterobimetallic isomers, [Zn_PDIFe_Cy(PDIeCy)(OTf)₄] (3) and [Fe_PDIZn_Cy(PDIeCy)(OTf)₄] (4), and a dizinc complex, [Zn₂(PDIeCy)(OTf)₄] (5). Olefin epoxidation by the series of complexes was investigated. The M-PDI site influences the reactivity of the M-cyclam, resulting in increased activity toward enones.