[Cp*Rh] compounds bearing 4,4′-disubstituted bpy ligands (Cp* = pentamethylcyclopentadienyl; bpy = bipyridine) have recently been shown to be tunable catalysts for hydrogen evolution. We have recently introduced nitro substituents onto bpy bound to [Cp*Rh] and find that these highly electron-withdrawing moieties induce marked changes in the electrochemical properties of the metal complex. We observe four quasi-reversible reductions, contrasting with two-electron reductions observed for most other [Cp*Rh] complexes. We have synthesized and isolated a singly reduced complex, and have characterized this species with electron paramagnetic resonance spectroscopy. We will discuss the electrochemical properties of this system, including potential-dependent spectroelectrochemical behavior.

Single-electron redox chemistry of [Cp*Rh] enabled by a nitrated bipyridine ligand

255th National Meeting (2018)

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