Fate of Oxidation States at Actinide Centers in Redox-Active Ligand Systems Governed by Energy Levels of 5 f Orbitals

被引：3

作者：

Takeyama, Tomoyuki ^{[1
,2
]}

Tsushima, Satoru ^{[3
,4
]}

Gericke, Robert ^{[3
]}

Kaden, Peter ^{[3
]}

Maerz, Juliane ^{[3
]}

Takao, Koichiro ^{[1
]}

机构：

[1] Tokyo Inst Technol, Inst Innovat Res, Lab Zero Carbon Energy, 2-12-1 N1-32,Meguro Ku, Tokyo 1528550, Japan

[2] Sanyo Onoda City Univ, Fac Engn, Dept Appl Chem, 1-1-1 Daigakudori, Yamaguchi 7560884, Japan

[3] Helmholtz Zentrum Dresden Rossendorf HZDR, Inst Resource Ecol, Bautzner Landstr 400, D-01328 Dresden, Germany

[4] Tokyo Inst Technol, Inst Innovat Res, Int Res Frontiers Initiat IRFI, 2-12-1 Ookayama,Meguro Ku, Tokyo 1528550, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2023年 / 29卷 / 69期

关键词：

actinide; crystal structures; ligands; neptunium; reduction; BRIDGED DIMERS; REDUCTION; URANYL; COMPLEXES; TRENDS; NP(V);

D O I：

10.1002/chem.202302702

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report the formation of a Np-IV complex from the complexation of (NpO22+)-O-VI with the redox-active ligand tBu-pdiop(2-)=2,6-bis[N-(3,5-di-tert-butyl-2-hydroxyphenyl)iminomethyl]pyridine. To the best of our knowledge, this is the first example of the direct complexation-induced chemical reduction of (NpO22+)-O-VI to Np-IV. In contrast, the complexation of (UO22+)-O-VI with tBu-pdiop(2-) did not induce the reduction of (UO22+)-O-VI, not even after the two-electron electrochemical reduction of [(UO2)-O-VI(tBu-pdiop)]. This contrast between the Np and U systems may be ascribed to the decrease of the energy of the 5 f orbitals in Np compared to those in U. The present findings indicate that the redox chemistry between (UO22+)-O-VI and (NpO22+)-O-VI should be clearly differentiated in redox-active ligand systems.

引用

页数：7

共 38 条

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