Probing the Framework Metal Dependent Properties of Actinide-Centered Polyoxoalkoxide Sandwich-Type Complexes

Development of a simple and scalable synthesis of (TBA)₃[W₅O₁₈MoNO] provides for the formation of the mixed-metal lacunary polyoxoalkoxide, (TBA)₂[W₄O₁₃(OMe)₄MoNO][Na(MeOH)]. This complex was used to synthesize a series of polyoxoalkoxide sandwich-type complexes with the general formula (TBA)₂[M{W₄O₁₃(OMe)₄MoNO}₂], where M = Zr(IV), Hf(IV), Th(IV), U(IV), and Np(IV). Compared to the analogous all-molybdenum complexes, the series have drastically different optical and redox properties. The results indicate that framework metal substitution acts as a tool for "orbital engineering", with Density Functional Theory (DFT) calculations revealing that the major consequence of incorporation of tungsten into the complexes is localization of LUMO and LUMO+1 on the molybdenum centers remaining in the molecule. The change in the distribution of the frontier orbitals translates to discrepancies in the electronic properties of the series. Given the rarity of polyoxometalate complexes featuring a U(V) ion, one electron oxidation of (TBA)₂[U(IV){W₄O₁₃(OMe)₄MoNO}₂] was pursued. Isolation of the corresponding U(V) centered sandwich-type complex is reported, only the second example of U(V)-polyoxometalate complex described to date.