Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization

The synthesis of a tetravalent neptunium amidinate [NpCl((S)-PEBA)₃] ( 1 ) ((S)-PEBA=(S,S)-N,N′-bis-(1-phenylethyl)-benzamidinate) is reported. This complex represents the first structurally characterized enantiopure transuranic compound. Reactivity studies with halide/pseudohalides yielding [NpX((S)-PEBA)₃] (X=F ( 2 ), Br ( 3 ), N₃ ( 4 )) have shown that the chirality-at-metal is preserved for all compounds in the solid state. Furthermore, they represent an unprecedented example of a structurally characterized metal–organic Np complex featuring a Np−Br ( 3 ) bond. In addition, 4 is the only reported tetravalent transuranic azide. All compounds were additionally characterized in solution using para-magnetic NMR spectroscopy showing an expected C₃-symmetry at low temperatures.     

ChemInform Abstract: Structure,Properties, and Theoretical Electronic Structure of UCuOP and NpCuOP.

The title compounds are prepared by solid state reaction of U or Np, Cu and/or CuO, and P at 1073—1273 K (evacuated silica tube, 96 h).     

Electromigration Studies of Carrier-Free 239Np(V) in Aqueos Solutions

Ion mobilities of carrier-free ²³⁹Np(V) have been measured in aqueous solutions, T = 298.1 (1) K. Ion mobilities of ²³⁹NpO₂ ⁺ and its dependencies on pH of acidic inert electrolytes have been measured. In alkaline solutions the stoichimetric hydrolysis constants of NpO₂(OH) as well as NpO₂(OH)₂ ^? have been obtained. Complex formations of ²³⁹Np(V) with oxalate, tartrate, sulphate, acetate and citrate ligands have been studied in neutral solutions.     

Spontaneous Chelation-Driven Reduction of the Neptunyl Cation in Aqueous Solution

Octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) siderophore analogues are known to be efficacious chelators of the actinide cations, and these ligands are also capable of facilitating both activation and reduction of actinyl species. Utilizing X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, as well as cyclic voltammetry measurements, herein, we elucidate chelation-based mechanisms for driving reactivity and initiating redox processes in a family of neptunyl–HOPO and CAM complexes. Based on the selected chelator, the ability to control the oxidation state of neptunium and the speed of reduction and concurrent oxo group activation was demonstrated. Most notably, reduction kinetics for the Np^VO₂^+//Np^IV redox couple upon chelation by the ligands 3,4,3-LI(1,2-HOPO) and 3,4,3-LI(CAM)₂(1,2-HOPO)₂ was observed to be faster than ever reported, and in fact quicker than we could measure using either X-ray absorption spectroscopy or electrochemical techniques.     

Applications of Alkali Metal Hydroxide Hydrofluxes to the Synthesis of Single-Crystal Ternary Actinide Oxides

Hydrofluxes are hydrated salts with melting points well below that of the dehydrated salt and boiling points well above that of water, affording a reaction medium, in which mild temperatures and pressures can be accessed for the synthesis of materials. Herein, the use of alkali metal hydroxide hydrofluxes for the synthesis of single crystal α-Na₂NpO₄ is described, and the single crystal X-ray structure of α-Na₂NpO₄, along with its X-ray absorption spectra and vibrational spectra, is reported. The ability to synthesize complex oxides of the actinides, in particular, transuranium materials, under mild conditions will serve to advance our ability to explore the structure–property relationships of the f elements.     

Subtle Interactions and Electron Transfer between UIII,NpIII, or PuIII and Uranyl Mediated by the Oxo Group

A dramatic difference in the ability of the reducing An^III center in AnCp₃ (An=U, Np, Pu; Cp=C₅H₅) to oxo‐bind and reduce the uranyl(VI) dication in the complex [(UO₂)(THF)(H₂L)] (L=“Pacman” Schiff‐base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At‐first contradictory electronic structural data are explained by combining theory and experiment. Complete one‐electron transfer from Cp₃U forms the U^IV‐uranyl(V) compound that behaves as a U^V‐localized single molecule magnet below 4 K. The extent of reduction by the Cp₃Np group upon oxo‐coordination is much less, with a Np^III‐uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np^IVU^V but single‐crystal X‐ray diffraction and SQUID magnetometry suggest a Np^III‐U^VI assignment. DFT‐calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu^III–U^VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions.     

Systematic DFT Study of Gas Phase and Solvated Uranyl and Neptunyl Complexes [AnO2X4]n (An: U,Np; X: F,Cl, OH,n = ‐2; X: H2O,n = +2).

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