Synthesis of arene-soluble mixed-metal uranium/zirconium complexes using the dizirconium nonaisopropoxide ligand.

ABSTRACT

The utility of polydentate monoanionic [Zr(2)(O(i)Pr)(9)](-) (dzni) in generating arene-soluble, mixed-metal Zr/U complexes is described. K[Zr(2)(O(i)Pr)(9)] reacts readily with UI(3)(THF)(4) to form [Zr(2)(O(i)Pr)(9)]UI(2)(THF), 1, in >90% yield. The integrity of the [[Zr(2)(O(i)Pr)(9)]U](2+) unit in 1 was examined by the reaction of 1 with K(2)C(8)H(8), which formed the organometallic complex [Zr(2)(O(i)Pr)(9)]U(C(8)H(8)), 2. In contrast, the reaction of K[Zr(2)(O(i)Pr)(9)] with UCl(4) did not form U(IV)-dzni complexes, and only the ligand exchange product, [UCl(2)(O(i)Pr)(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.