Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization. Issue 41 (25th June 2020)

• Record Type: Journal Article
• Authors: Fichter, Sebastian; Kaufmann, Sebastian; Kaden, Peter; Brunner, Tobias S.; Stumpf, Thorsten; Roesky, Peter W.; März, Juliane
• Is Part Of: Chemistry. Volume 26:Issue 41(2020)
• Page Start: 8867
• Page End: 8870
• Publication Date: 2020-06-25
• Subjects: actinides -- amidinates -- coordination chemistry -- neptunium -- transuranium chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202001865
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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. Abstract : Enantiopure transuranic complexes : The first structurally characterized enantiopure complexes of neptunium have been synthesized. Starting from a chloro tris(amidinate) complex unprecedented neptunium(IV) fluoro, ‐bromo and ‐azido compounds could be yielded and characterized in solution and in the solid state (see scheme).