Cation-Cation Interaction in Np(V) Perchlorates and Their Electronic Absorption Spectra.

Four new Np(V) perchlorate complexes of the composition [NpO(HO)]ClO (orthorhombic) (), [(NpO)(ClO)(HO)]ClO·HO (), [(NpO)(UO)(HO)](ClO) (), and [(NpO)Cl(HO)]ClO·2HO () have been synthesized and structurally characterized. The structure of previously known monoclinic modification of NpOClO·4HO () has been determined at 100 K. The coordination environment of Np and U atoms in compounds - is pentagonal bipyramids.

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

Five new mixed-valence Np/An molybdates of the composition [C(NH)][(NpO)(NpO)(MoO)(HO)]·HO (), [C(NH)][(NpO)(NpO)(MoO)(HO)]·3HO (), Na[(NpO)(PuO)(MoO)(HO)]·HO (), Na[(NpO)(UO)(MoO)]·13HO (), and LiNa[(NpO)(NpO)(MoO)(HO)]·4HO () have been synthesized and structurally characterized. The coordination polyhedra of the Np and An atoms in compounds - are pentagonal bipyramids. The basis of structures - is anionic layers of the composition [(NpO)(AnO)(MoO)(HO)].

Neptunium(V) Isothiocyanate Complexes with 4'-Aryl-Substituted 2,2':6',2″-Terpyridines and ,-Dimethylacetamide as Molecular Ligands.

New complexes of neptunyl(V) isothiocyanate with 4'-aryl-substituted 2,2':6',2″-terpyridines (Terpy) and ,-dimethylacetamide (DMA) were obtained: [(NpO)(4'-Ph-Terpy)(DMA)(NCS)]·DMA, [(NpO)(4'-(4-(CF)CH)-Terpy)(DMA)(NCS)]·2HO·DMA, [(NpO)(4'-(3-BrCH)-Terpy)(DMA)(NCS)]·DMA, and [(NpO)(4'-(2-(COOH)CH)-Terpy)(DMA)(NCS)]·DMA. The structures of the compounds were determined with X-ray diffraction analysis. The neptunium coordination polyhedra were found to be pentagonal bipyramids with O atoms of the NpO groups in the apical positions and the equatorial planes formed by three N atoms of the terpyridine ligand, a N atom of the isothiocyanate anion, and an O atom of DMA.

The reaction chemistry of plutonyl(VI) chloride complexes with triphenyl phosphineoxide and triphenyl phosphinimine.

The reaction between Ph(3)PO dissolved in acetone and "PuO(2)Cl(2)" in dilute HCl resulted in the formation of [PuO(2)Cl(2)(Ph(3)PO)(2)]. Crystallographic characterization of the acetone solvate revealed the expected axial trans plutonyl dioxo, with trans Cl and Ph(3)PO in the equatorial plane. Spectroscopic analyses ((31)P NMR, (1)H NMR, and vis/nIR) indicate the presence of both cis and trans isomers in solution, with the trans isomer being more stable.

Structure determination of neptunium(VI) mu3-hydroxobenzoate, [(NpO2)2(mu3-OH)2(H5C6COO)2] x 2 H2O.

Neptunium(VI) benzoate with mu(3)-OH(-) has been isolated and studied by the X-ray method. The main structural motive in the crystal is corrugated ribbons [(NpO(2))(2)(mu(3)-OH)(2)(C(7)H(5)O(2))(2)](n) extended along the c axes in which three neptunium pentagonal bipyramids are linked through the mu(3)-OH(-) ligand. The benzoate ions are arranged at both sides of the ribbons, and each anion binds two adjacent NpO(2).