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 C$_{3}$‐symmetry at low temperatures.