Insights into the Electronic Structure of a U(IV) Amido and U(V) Imido Complex.

Reaction of the N-heterocylic carbene ligand PrIm (L ) and lithium bis(trimethylsilyl)amide (TMSA) as a base with UCl resulted in U(IV) and U(V) complexes. Uranium's +V oxidation state in (HL ) [U(V)(TMSI)Cl ] (TMSI=trimethylsilylimido) (2) was confirmed by HERFD-XANES measurements. Solid state characterization by SC-XRD and geometry optimisation of [U(IV)(L ) (TMSA)Cl ] (1) indicated a silylamido ligand mediated inverse trans influence (ITI). The ITI was examined regarding different metal oxidation states and was compared to transition metal analogues by theoretical calculations.