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

Five new mixed-valence Np V /An VI molybdates of the composition [C(NH 2 ) 3 ] 3 [(Np V O 2 )(Np VI O 2 )(MoO 4 ) 3 (H 2 O)]·H 2 O ( 1 ), [C(NH 2 ) 3 ] 3 [(Np V O 2 )(Np VI O 2 )(MoO 4 ) 3 (H 2 O)]·3H 2 O ( 2 ), Na 3 [(Np V O 2 )(Pu VI O 2 )(MoO 4 ) 3 (H 2 O)]· n H 2 O ( 3 ), Na 6 [(Np V O 2 ) 2 (U VI O 2 )(MoO 4 ) 5 ]·13H 2 O ( 4 ), and LiNa 2 [(Np V O 2 )(Np VI O 2 ) 2 (MoO 4 ) 4 (H 2 O)]·4H 2 O ( 5 ) have been synthesized and structurally characterized. The coordination polyhedra of the Np V and An VI atoms in compounds 1 - 5 are pentagonal bipyramids. The basis of structures 1 - 3 is anionic layers of the composition [(Np V O 2 )(An VI O 2 )(MoO 4 ) 3 (H 2 O)] n 3 n - . Three crystallographically independent molybdate ions are tridentate-bridging ligands. The water molecule, which is a part of the anion layer, is coordinated to the Np V 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 [(Np V O 2 ) 2 (U VI O 2 )(MoO 4 ) 5 ] n 6 n - , 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.