The divergent reactivity of U/Np(III) and U/Np(IV) organoactinide complexes is explored. Reduction of AnCl4(DME)x, [An = (U (x=0); Np (x=2)], with potassium dimethylbenzylamide, results in rare An(III) alkyl complexes, (An[η4-Me2NC(H)C6H5]3). Unlike the U(III) complex, the neptunium analog can be used to access subsequent Np(III) complexes. The reaction of An[η4-Me2NC(H)C6H5]3 with a sterically demanding dithiocarboxylic acid (HS2C(2,6-Mes2-C6H3) results in oxidation to U(IV), but the Np analog maintains the +3 oxidation state. An(IV) (An = U, Np) aryl oxide complexes, An[ArOSeOAr]2(THF)2, were synthesized from AnCl4(DME)x and two equivalents of K2(ArOSeOAr), (ArOSeOAr = [(4,6-tBu2C6H2O)2Se]2−). Reactivity with p-benzoquinone resulted in a U(V)-U(V) dimer, but no change was observed with the neptunium complex.

Organoactinide complexes of uranium and neptunium

2019 Fall National Meeting

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