Synthesis of Imido Analogs of the Uranyl Ion

Abstract

Here we describe the synthesis of two imido analogs of the uranyl ion, UO 2+ 2 , in which the oxygens are replaced by divalent alkyl or aryl nitrogen groups: U(N t Bu) 2 I 2 (THF) 2 (1) and U(NPh) 2 I 2 (THF) 3 (2) (where t Bu is tert -butyl and THF is tetrahydrofuran). Both compounds have been fully characterized by standard analytical techniques, including x-ray crystallography, and the chemical bonding between the metal center and the nitrogen ligands was quantified by using hybrid density functional theory calculations. As expected for a uranyl analog, these complexes exhibit linear N-U-N linkages and very short U-N bonds. In addition, the theoretical calculations show strong involvement of the 5f and 6d electrons in the U-N bonding.