Complexation of Hexavalent Neptunium(VI) with Oxydiacetic Acid and Its Amide Derivatives in Aqueous Solution: Spectrophotometry and DFT Calculations

Xu, Lei1,2; Zhao, Xiao-Kun3; Cao, Hong1; Hu, Han-Shi4; Li, Jun4; Chen, Jing1; Xu, Chao1

2024-03-26

10.1021/acs.inorgchem.3c04221

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

Unfolding the solution coordination chemistry of high-valent transuranium elements with the "CHON"-type ligands is important to understand the fundamental chemistry of actinides and to design more efficient extractants for partitioning of transuranium elements in advanced nuclear fuel cycles. Here, the complexation of a hexavalent neptunyl ion (NpO22+ or Np(VI)) with oxydiacetic acid (ODA) has been systematically investigated in comparison with its amide analogues N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) and N,N,N ',N '-tetramethyl-3-oxa-glutaramide (TMOGA) both experimentally and computationally. The formation of both 1:1 and 1:2 complexes between Np(VI) and the three ligands was identified by spectrophotometry, and their stability constants were obtained and compared with those of hexavalent U(VI) and Pu(VI). The corresponding bonding nature is elucidated by using energy decomposition analysis (EDA), electrostatic potential (ESP), ELF contours, and natural orbitals for chemical valence (NOCV) methods, which shows that the Np-O bonds are essentially ionic in character and the unoccupied 6d orbitals of Np play a key role in enhancing the covalent interactions between Np(VI) and the three ligands.

SCI ; EI

英语

其他

National Natural Science Foundation of China["22325603","U2067213","22206168","22076095","22222605"]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:001191241800001

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Tsinghua Univ, Inst Nucl & New Energy Technol, Beijing 100084, Peoples R China
2.Zhejiang Univ, Inst Nucl Agr Sci, Key Lab Nucl Agr Sci, Minist Agr & Zhejiang Prov, Hangzhou 310058, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China

Xu, Lei,Zhao, Xiao-Kun,Cao, Hong,et al. Complexation of Hexavalent Neptunium(VI) with Oxydiacetic Acid and Its Amide Derivatives in Aqueous Solution: Spectrophotometry and DFT Calculations[J]. INORGANIC CHEMISTRY,2024,63(14).

Xu, Lei.,Zhao, Xiao-Kun.,Cao, Hong.,Hu, Han-Shi.,Li, Jun.,...&Xu, Chao.(2024).Complexation of Hexavalent Neptunium(VI) with Oxydiacetic Acid and Its Amide Derivatives in Aqueous Solution: Spectrophotometry and DFT Calculations.INORGANIC CHEMISTRY,63(14).

Xu, Lei,et al."Complexation of Hexavalent Neptunium(VI) with Oxydiacetic Acid and Its Amide Derivatives in Aqueous Solution: Spectrophotometry and DFT Calculations".INORGANIC CHEMISTRY 63.14(2024).