Mixed-Valence Np^V/An^VI Molybdate Complexes with Single-Charge Outer-Sphere Cations

Abstract

Five new mixed-valence NpV/AnVI molybdates of the composition [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·H2O (1), [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·3H2O (2), Na3[(NpVO2)(PuVIO2)(MoO4)3(H2O)]·nH2O (3), Na6[(NpVO2)2(UVIO2)(MoO4)5]·13H2O (4), and LiNa2[(NpVO2)(NpVIO2)2(MoO4)4(H2O)]·4H2O (5) have been synthesized and structurally characterized. The coordination polyhedra of the NpV and AnVI atoms in compounds 1–5 are pentagonal bipyramids. The basis of structures 1–3 is anionic layers of the composition [(NpVO2)(AnVIO2)(MoO4)3(H2O)] n 3n–. Three crystallographically independent molybdate ions are tridentate-bridging ligands. The water molecule, which is a part of the anion layer, is coordinated to the NpV atom. The anionic layers in complexes 2 and 3 have the same structure, different from 1. The basis of structure 4 is anionic layers of the composition [(NpVO2)2(UVIO2)(MoO4)5] n 6n–, the structure of which differs from the structure of anionic layers in 1–3. Complex 5 has a three-dimensional (3D) structure. The spectra of all compounds in the UV–visible and IR ranges were measured and analyzed.