Protonation of certain cyclopentadienyl (Cp) and pentamethylcyclopentadienyl (Cp*) complexes has recently been shown to result in proton transfer to the ligand rather than formation of metal hydride species. Cp*Rh(bpy) (bpy = 2,2′-bipyridyl) can generate H<sub>2</sub> in the presence of a proton source via an intermediate bearing a [Cp*H] ligand. We find that the substitution pattern of the bpy ligand governs the properties of the [Cp*H] complexes, and are thus working to synthesize new complexes bearing other bidentate ligands to further modulate reactivity on these platforms. Here, we will describe the synthesis and characterization of a new family of [Cp*Rh] compounds that are ligated by a bidentate phosphine, including a monohydride compound. Chemical and electrochemical studies conducted both with and without added acid have been used to explore several activation modes of the monohydride compound. Recent results from reactivity and isotope labeling studies will be discussed.

Chemical and electrochemical activation modes of a [Cp*Rh] monohydride

256th National Meeting (2018)

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