Evidence for Charge Delocalization in Diazafluorene Ligands Supporting Low-Valent [Cp*Rh] Complexes**

Ligands based upon the 4,5-diazafluorene core are an important class of emerging ligands in organometallic chemistry, but the structure and electronic properties of these ligands have received less attention than they deserve. Here, we show that 9,9′-dimethyl-4,5-diazafluorene (Me₂daf) can stabilize low-valent complexes through charge delocalization into its conjugated π-system. Using a new platform of Cp*Rh] complexes with three accessible formal oxidation states (+III, +II, and +I), we show that the methylation in Me₂daf is protective, blocking Brønsted acid-base chemistry commonly encountered with other daf-based ligands. Electronic absorption spectroscopy and single-crystal X-ray diffraction analysis of a family of eleven new compounds, including the unusual Cp*Rh(Me₂daf), reveal features consistent with charge delocalization driven by π-backbonding into the LUMO of Me₂daf, reminiscent of behavior displayed by the workhorse 2,2′-bipyridyl ligand. Taken together with spectrochemical data demonstrating clean conversion between oxidation states, our findings show that 9,9′-dialkylated daf-type ligands are promising building blocks for applications in reductive chemistry and catalysis.