Density functional theory (DFT) calculations on four known and seven hypothetical U(II) complexes indicate the importance of coordination geometry in favoring 5f6d versus 5f electronic ground states. The known [Cp″U], [CpU], and [U(NR)] [Cp″ = CH(SiMe), Cp = CMeH, and R = SiMe] anions were found to have 5f6d ground states, while a 5f ground state was found for the known compound (NHAr)U. The UV-visible spectra of the known 5f6d compounds were simulated via time-dependent DFT and are in qualitative agreement with the experimental spectra. For the hypothetical U(II) compounds, the 5f6d configuration is predicted for [U(CHR)], [U(HBH)], [U(OAr')], and [(CH)U] (OAr' = O-CHBu-2,6-Me-4). In the case of [U(bnz')] (bnz' = CH-CHBu-4), a 5f configuration with a ligand-based radical was found as the ground state.
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