Inorganic Chemistry, Vol.40, No.26, 6725-6730, 2001
Synthesis of arene-soluble mixed-metal uranium/zirconium complexes using the dizirconium nonaisopropoxide ligand
The utility of polydentate monoanionic [Zr-2((OPr)-Pr-i)(9)](-) (dzni) in generating arene-soluble, mixed-metal Zr/U complexes is described. K[Zr-2((OPr)-Pr-i)(9)] reacts readily with UI3(THF)(4) to form [Zr-2((OPr)-Pr-i)(9)]UI2(THF), 1, in > 90% yield. The integrity of the {[Zr-2((OPr)-Pr-i)(9)]U}(2+) unit in 1 was examined by the reaction of 1 with K2C8H8, which formed the organometallic complex [Zr-2((OPr)-Pr-i)(9)]U(C8H8), 2. In contrast, the reaction of K[Zr-2((OPr)-Pr-i)(9)] with UCl4 did not form U(IV)-dzni complexes, and only the ligand exchange product, [UCl2((OPr)-Pr-i)(2)(DME)](2), 3, was isolated. The effect of the dzni ligand on the electrochemistry and near-infrared spectroscopy of U(III) is also described.