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Complexation of NpO2+ with Amine-Functionalized Diacetamide Ligands in Aqueous Solution: Thermodynamic, Structural, and Computational Studies

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [3];  [4];  [2];  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Harbin Engineering Univ. (China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  4. Univ. di Udine (Italy). Lab. di Chimica, via delle Scienze
+ Show Author Affiliations
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, NpO2L+ and NpO2L2+, 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 Nd3+ and UO22+, the ligands coordinate to NpO2+ in a tridentate mode through the amine nitrogen and two oxygen atoms of the amide groups. Furthermore, computational results, in conjunction with spectrophotometric data, verify that the 1:2 complexes (NpO2(L)2+) in aqueous solutions are highly symmetric with Np at the inversion center, so that the f-f transition of Np(V) is forbidden and NpO2(L)2+ does not display significant absorption in the near-IR region.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1783092
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorption
chemical structure
complexation
extended x-ray absorption fine structure
ligands