Electron and proton reservoir complexes: thermodynamic basis for C-H activation and applications in redox and dendrimer chemistry.

Abstract

This Account focuses on fundamental aspects and applications of the concept of "electron and proton reservoirs". Permethylated electron reservoir iron sandwich complexes, which were known to be excellent reducing agents in their neutral 19e Fe(I) form, have recently been shown to be stable strong oxidants in their dicationic 17e Fe(III) form. Thermodynamic, mechanistic, and synthetic aspects of the redox chemistry of these and related organoiron complexes are summarized. Proton reservoir properties of these complexes are due to enhanced acidity in their cationic form and result in an original type of activation: perfunctionalization leading to dendritic cores and useful metallodendrimers of variable topology.