[AnI3(THF)4] (An = Np, Pu) Preparation Bypassing An0 Metal Precursors: Access to Np3+/Pu3+ Nonaqueous and Organometallic Complexes

Direct comparison of homologous molecules provides a foundation from which to elucidate both subtle and patent changes in reactivity patterns, red ox processes, and bonding properties across a series of elements. While trivalent molecular U chemistrY is richly developed, analogous Np or Pu research has long been hindered by synthetic routes often requiring scarcely available metallic-phase source material, high-temperature solidstate reactions producing poorly soluble binary halides, or the use of pyrophoric reagents. The development of routes to nonaqueous Np3+/Pu3+ from widely available precursors can potentially transform the scope and pace f research into actinide PeriodicitY. Here, aqueous stocks of An(4+) (An = Np, Pu) are dehydrated towell-defined [AnCl(4)(DME)(2)] (DME = 1,2-dimethoxyethane) and then a single-step halide exchange/reduction employing Me3SCl Produces [AnI(3)(TFIF)(4)] (THF = tetrahYdrcifilrari) in a high to fnearly quantitative crystalline yield (with I-2 and Me3SiCI as easily removed by Broducts)-We demonstrate the synthetic, utility of these An-iodide molecules, prepared by metal(0)-free routes, through characterization of archetypal complexes' incbluodithngmothtiefstrairsesil lan-iide, [Np{N(SiMe3)(2)}(3)], and bent metaIl ceiles,[An(C5Me5)(2) (I)(THF)] (An = Np, Pu)-chosen because,ubiquitousY in Th, U, and lanthanide research. The synthesis of [Np{N(Se=PPh2)(2)}(3) is also reported, series that now extends from U to Am and is the first characterized Np3+-Se bond.

Automated summary

Direct comparison of homologous molecules allows the elucidation of changes in reactivity patterns, redox processes, and bonding properties across a series of elements. Synthetic routes for Np and Pu research have been hindered, but the development of new methods using widely available precursors can potentially transform research into actinide periodicity. The synthesis of An-iodide molecules and the characterization of Np3+-Se bonds represent significant advancements in the field.