Investigating Recurrent Matere Bonds in Pertechnetate Compounds.

In this manuscript we evaluate the X-ray structure of five new pertechnetate derivatives of general formula [M(H2O)4(TcO4)2], M=Mg, Co, Ni, Cu, Zn (compounds 1-5) and one perrhenate compound Zn(H2O)4(ReO4)2 (6). In these complexes the metal center exhibits an octahedral coordination with the pertechnetate units as axial ligands. All compounds exhibit the formation of directional Tc⋅⋅⋅O Matere bonds (MaBs) that propagate the [M(H2O)4(TcO4)2], into 1D supramolecular polymers in the solid state. Such 1D polymers are linked, generating 2D layers, by combining additional MaBs and hydrogen bonds (HBs). Such concurrent motifs have been analyzed theoretically, suggesting the noncovalent σ-hole nature of the MaBs. The interaction energies range from weak (~ -2 kcal/mol) for the MaBs to strong (~ -30 kcal/mol) for the MaB+HB assemblies, where HB dominates. In case of M=Zn, the corresponding perrhenate Zn(H2O)4(ReO4)2 complex, has been also synthesized for comparison purposes, resulting in the formation of an isostructural X-ray structure, corroborating the structure-directing role of Matere bonds.

Pertechnetates - A Structural Study Across the Periodic Table.

The number of crystal structures of pertechnetates derived from aqueous solutions has been expanded from seven to over 30. We report the conversion of NH4TcO4 to aqueous HtcO4 via acidic cation exchange. This is followed by the synthesis and structural elucidation of pertechnetate salts of alkaline earth (AE), transition metal I and lanthanoids (Ln) elements. Various degrees of hydration and coordination are discussed. Where possible, a comparison with the perrhenate homologues is made. The described syntheses and materials may be used as novel starting materials for extended technetium research.

Neptunium Alkoxide Chemistry: Expanding Alkoxides to the Transuranium Elements.

Two oxo-containing neptunium(IV) tert-butoxides, [Np3O(OtBu)10] (1) and [K4Np2O(OtBu)10] (2), were synthesized using the ligand substitution between neptunium(IV) silylamides and HOtBu, whereas the salt metathesis between [NpCl4(DME)2] (DME = dimethoxyethane) and various amounts of LiOtBu resulted in the formation of oxo-free alkoxides [Np(OtBu)4(py)2] (3; py = pyridine) and [Li(THF)]2[Np(OtBu)6] (4; THF = tetrahydrofuran). These complexes are the first structurally characterized neptunium(IV) alkoxides using single-crystal X-ray diffraction and solid-state absorption spectroscopy, which provide data for the development of anhydrous metal-organic neptunium chemistry.

Two Neptunium(III) Mellitate Coordination Polymers: Completing the Series Np-Cf of Trans-Uranic An(III) Mellitates.

Two neptunium(III) mellitates, 237Np2(mell)(H2O)9·1.5H2O (Np-1α) and 237Np2(mell)(H2O)8·2H2O (Np-1ß), have been synthesized from 237NpCl4(dme)2 by reduction with KC8 and subsequent reaction with an aqueous solution of mellitic acid (H6mell). Characterization by single-crystal X-ray crystallography and UV-vis-NIR spectroscopy confirms that the neptunium is in its +3 oxidation state and both polymorphs are isostructural to the previously reported plutonium mellitates. Of the two morphologies, Np-1α is indefinitely stable in air, while Np-1ß slowly oxidizes over several months. This is due to the change in the energy of the metal-ligand charge-transfer absorption exhibited by these compounds attributed to differing numbers of carboxylate bonds to Np(III), where in Np-1ß the energy is low enough to result in spontaneous oxidation.

Synthesis, characterization, and high-pressure studies of a 3D berkelium(III) carboxylate framework material.

A berkelium(III) mellitate, Bk2[C6(CO2)6](H2O)8·2H2O, was synthesized and rapidly crystallized by reacting mellitic acid, C6(CO2H)6, and BkBr3·nH2O in an aqueous medium. Single crystal X-ray diffraction shows that the compound crystallizes as a three-dimensional framework isostructural with Pu(III), Am(III), and Cm(III) mellitates. UV-vis-NIR spectroscopic studies as a function of pressure were performed using a diamond anvil cell and show that the 5f → 5f transitions of Bk3+ display enhanced hypsochromic shifting when compared to other An(III) mellitates.

Ammonium Pertechnetate in Mixtures of Trifluoromethanesulfonic Acid and Trifluoromethanesulfonic Anhydride.

Ammonium pertechnetate reacts in mixtures of trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid under final formation of ammonium pentakis(trifluoromethanesulfonato)oxidotechnetate(V), (NH4 )2 [TcO(OTf)5 ]. The reaction proceeds only at exact concentrations and under the exclusion of air and moisture via pertechnetyl trifluoromethanesulfonate, [TcO3 (OTf)], and intermediate TcVI species. 99 Tc nuclear magnetic resonance (NMR) has been used to study the TcVII compound and electron paramagnetic resonance (EPR), 99 Tc NMR and X-ray absorption near-edge structure (XANES) experiments indicate the presence of the reduced technetium species. In moist air, (NH4 )2 [TcO(OTf)5 ] slowly hydrolyses under formation of the tetrameric oxidotechnetate(V) (NH4 )4 [{TcO(TcO4 )4 }4 ] ⋅10 H2 O. Single-crystal X-ray crystallography was used to determine the solid-state structures. Additionally, UV/Vis absorption and IR spectra as well as quantum chemical calculations confirm the identity of the species.

Heterobimetallic uranyl(VI) alkoxides of lanthanoids: formation through simple ligand exchange.

Lanthanoid and actinoid silylamides are versatile starting materials. Herein we show how a simple ligand exchange with tert-butanol leads to the formation of the first trimeric heterobimetallic uranyl(VI)-lanthanoid(III) alkoxide complexes. The µ3 coordination of the endogenous uranyl oxo atom results in a significant elongation of the bond length and a significant deviation from the linear uranyl arrangement.