Single-Electron Redox Chemistry on the [Cp*Rh] Platform Enabled by a Nitrated Bipyridyl Ligand

[Cp*Rh] complexes (Cp* = pentamethylcyclopentadienyl) are attracting renewed interest in coordination chemistry and catalysis, but these useful compounds often undergo net two-electron redox cycling that precludes observation of individual one-electron reduction events. Here, we show that a [Cp*Rh] complex bearing the 4,4'-dinitro-2,2'-bipyridyl ligand (dnbpy) (3) can access a distinctive manifold of five oxidation states in organic electrolytes, contrasting with prior work that found no accessible reductions in aqueous electrolyte. These states are readily generated from a newly isolated and fully characterized rhodium(III) precursor complex 3, formulated as [Cp*Rh(dnbpy)Cl]PF₆. Single-crystal X-ray diffraction (XRD) data, previously unavailable for the dnbpy ligand bound to the [Cp*Rh] platform, confirm the presence of both [η⁵-Cp*] and [κ²-dnbpy]. Four individual one-electron reductions of 3 are observed, contrasting sharply with the single two-electron reductions of other [Cp*Rh] complexes. Chemical preparation and the study of the singly reduced species with electronic absorption and electron paramagnetic resonance spectroscopies indicate that the first reduction is predominantly centered on the dnbpy ligand. Comparative cyclic voltammetry studies with [NBu₄][PF₆] and [NBu₄][Cl] as supporting electrolytes indicate that the chloride ligand can be lost from 3 by ligand exchange upon reduction. Spectroelectrochemical studies with ultraviolet (UV)-visible detection reveal isosbestic behavior, confirming the clean interconversion of the reduced forms of 3 inferred from the voltammetry with [NBu₄][PF₆] as supporting electrolyte. Electrochemical reduction in the presence of triethylammonium results in an irreversible response, but does not give rise to catalytic H₂ evolution, contrasting with the reactivity patterns observed in [Cp*Rh] complexes bearing bipyridyl ligands with less electron-withdrawing substituents.