Ligand-Based Storage of Protons and Electrons in Dihydrazonopyrrole Complexes of Nickel

Abstract

A newly developed dihydrazonopyrrole ligand and corresponding Ni complexes have been synthesized and thoroughly characterized. Electrochemical studies and chemical reactivity tests show that these complexes can reversibly store both electrons and protons, or equivalently H-atoms, via ligand-based events. The stored H-atom equivalent can be transferred to small molecules such as acetonitrile or oxygen. Furthermore, this series of complexes can adopt a variety of different coordination modes. In addition to one e^- reactivity, the two e^- electrophilic oxidation of phosphines is also demonstrated. Taken together, these results show that dihydrazonopyrrole complexes represent a geometrically and electronically flexible scaffold for controlling the flow of both electrons and protons.

Keywords: hydrogen transfer; non-innocent ligands; radicals; tridentate ligands.