Redox active amido-bridged Cu_2N_2 diamond core complexes supported by thioether and phosphine ligands

Abstract

A series of novel Cu_2N_2 diamond core structures supported by S_2N- and P_2N- ligands have been prepared. These diamond core systems exhibit a reversible 1-electron redox process between a reduced Cu^1Cu^1 and a class Ill delocalized Cu^(1.5)Cu^(1.5) state. Solid-state molecular structures have been obtained of both the oxidized and reduced forms of this system. Minimal overall structural reorganization is observed between the reduced and oxidized states, though a marked CuCu compression (-0.13 Å) does occur upon oxidation. As a result, unusually facile electron self-exchange arises. Magnetic, electrochemical and spectroscopic data, as well as their reactivity, will be discussed.