Complexation of NpO 2 + with Amine-Functionalized Diacetamide Ligands in Aqueous Solution: Thermodynamic, Structural, and Computational Studies

• Published in: Inorganic chemistry 2018-06, Vol.57 (12), p.6965-6972
• Main Authors: Gao, Yang, Dau, Phuong V, Parker, Bernard F, Arnold, John, Melchior, Andrea, Zhang, Zhicheng, Rao, Linfeng
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.8b00654

Complexation of Np(V) with three structurally related amine-functionalized diacetamide ligands, including 2,2'-azanediylbis( N, N'-dimethylacetamide) (ABDMA), 2,2'-(methylazanediyl)bis( N, N'-dimethylacetamide) (MABDMA), and 2,2'-(benzylazanediyl)bis( N, N'-dimethylacetamide) (BnABDMA), in aqueous solutions was investigated. The stability constants of two successive complexes, namely, NpO L and NpO L , where L stands for the ligands, were determined by absorption spectrophotometry. The results suggest that the stability constants of corresponding Np(V) complexes follow the trend: MABDMA > ABDMA ≈ BnABDMA. The data are discussed in terms of the basicity of the ligands and compared with those for the complexation of Np(V) with an ether oxygen-linked diacetamide ligand. Extended X-ray absorption fine structure data indicate that, similar to the complexation with Nd and UO , the ligands coordinate to NpO in a tridentate mode through the amine nitrogen and two oxygen atoms of the amide groups. Computational results, in conjunction with spectrophotometric data, verify that the 1:2 complexes (NpO (L) ) in aqueous solutions are highly symmetric with Np at the inversion center, so that the f-f transition of Np(V) is forbidden and NpO (L) does not display significant absorption in the near-IR region.