Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex

Addition of 1 equiv of Li(Ar2nacnac) (Ar2nacnac = (2,6-iPr2C6H3)NC(Me)CHC(Me)N(2,6-iPr2C6H3))
to an Et2O suspension of UO2Cl2(THF)3 generates the uranyl dimer [UO2(Ar2nacnac)Cl]2 (1) in good yield.
A second species can be isolated in low yield from the reaction mixtures of 1, namely [Li(OEt2)2][UO2(Ar2nacnac)Cl2] (2). The structures of both 1 and 2 have been confirmed by X-ray crystallography. Complex 1
reacts with Ph3PO to generate UO2(Ar2nacnac)Cl(Ph3PO) (3). In addition, 1 reacts with AgOTf and either
1 equiv of DPPMO2 or 2 equiv of Ph2MePO to provide [UO2(Ar2nacnac)(DPPMO2)][OTf] (4) and [UO2(Ar2nacnac)(Ph2MePO)2][OTf] (5), respectively. Both 4 and 5 have been fully characterized, including analysis
by X-ray crystallography and cyclic voltammetry. Reduction of 4 with Cp2Co provides UO2(Ar2nacnac)(CH{Ph2PO}2) (6), a uranyl(VI) complex that is generated by the formal loss of H• from the DPPMO2 ligand.
Labeling studies have been performed in an attempt to elucidate the mechanism of hydrogen loss. In
contrast, reduction of 5 with Cp2Co provides UO2(Ar2nacnac)(Ph2MePO)2 (7), a rare example of a uranyl(V) complex. As expected, the solid-state molecular structure of 7 reveals slightly longer U−O(oxo) bond
lengths relative to 5. Furthermore, complex 7 can be converted back into 5 by oxidation with AgOTf in
toluene.