Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

摘要

The terminal actinide fluoride bonds in (C5Me5)2ThF2(py) (py?=?pyridine) and (C5Me5)2UF2(O=PR3) (R?=?Me, Ph) react with two equivalents of Me3SiN3in toluene to form the polymeric thorium bis(azide), [(C5Me5)2Th(N3)2]∞, and a new class of monometallic uranium bis(azide) complexes, (C5Me5)2U(N3)2(O=PR3), respectively. Full characterization of the novel complexes (C5Me5)2ThF2(py) and (C5Me5)2UF2(O=PR3) are reported, including the solid-state structures of (C5Me5)2ThF2(py) and (C5Me5)2U(N3)2(O=PPh3). Electronic absorption spectral data are also reported for (C5Me5)2AnF2(py) (An?=?Th, U) and (C5Me5)2U(N3)2(O=PR3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.