Inorganic Chemistry, Vol.51, No.11, 6190-6199, 2012
Observation of the Inverse Trans Influence (ITI) in a Uranium(V) Imide Coordination Complex: An Experimental Study and Theoretical Evaluation
An inverse trans influence has been observed in a high-valent U(V) imide complex, [(((ArO)-Ar-Ad)(3)N)U(NMes)]. A thorough theoretical evaluation has been employed in order to corroborate the ITI in this unusual complex. Computations on the target complex, [(((ArO)-Ar-Ad)(3)N)U(NMes)], and the model complexes [(((ArO)-Ar-Me)(3)N)U(NMes)] and [(NMe3)(OMe2)(OMe)(3)U(NPh)] are discussed along with synthetic details and supporting spectroscopic data. Additionally, the syntheses and full characterization data of the related U(V) trimethylsilylimide complex [(((ArO)-Ar-Ad)(3)N)U(NTMS)] and U(IV) azide complex [(((ArO)-Ar-Ad)(3)N)U(N-3)] are also presented for comparison.