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.