Wedal Justin C, Furche Filipp, Evans William J
Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
Inorg Chem. 2021 Nov 1;60(21):16316-16325. doi: 10.1021/acs.inorgchem.1c02161. Epub 2021 Oct 13.
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.
对四种已知的和七种假设的U(II)配合物进行的密度泛函理论(DFT)计算表明，配位几何结构对于5f6d基态和5f基态的形成具有重要影响。已知的[Cp″U]、[CpU]和[U(NR)] [Cp″ = CH(SiMe)，Cp = CMeH，R = SiMe]阴离子被发现具有5f6d基态，而已知化合物(NHAr)U则具有5f基态。通过含时密度泛函理论对已知的5f6d化合物的紫外可见光谱进行了模拟，结果与实验光谱在定性上一致。对于假设的U(II)化合物，预测[U(CHR)]、[U(HBH)]、[U(OAr')]和[(CH)U] (OAr' = O-CHBu-2,6-Me-4)具有5f6d构型。在[U(bnz')] (bnz' = CH-CHBu-4)的情况下，发现具有基于配体的自由基的5f构型为基态。
