Dovrat Gev, Pevzner Svetlana, Berthon Claude, Lerner Ana, Maimon Eric, Vainer Radion, Karpasas Mark, Ben-Elyiahu Yeshayahu, Moisy Philippe, Bettelheim Armand, Zilbermann Israel
Energy Engineering Department, Ben-Gurion University of the Negev Beer-Sheva, Beer-Sheva, 84105, Israel.
Chemistry Department, Nuclear Research Centre Negev, IL-84190, Beer-Sheva, Israel.
Chemistry. 2021 Jun 4;27(32):8264-8267. doi: 10.1002/chem.202005350. Epub 2021 May 7.
Two new aqueous U complexes were synthesized by the interaction between the tetravalent uranium cation and the (1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid) (DOTP) macrocyclic ligand. Two distinct homonuclear complexes were identified; the first was characterized by X-ray crystallography as a unique "out-of-cage", [U(DOTPH ) ] complex, in which the U cation is octa-coordinated to 4 phosphonic arms from each ligand in a square anti-prism geometry, with a C symmetry. The second is the "in-cage" [U(DOTPH )] complex, in which the tetravalent cation is located between the macrocycle O and N planes. With the help of UV-Vis absorption, H/ P NMR, ATR-IR, and MALDI-TOFMS analytical techniques, the chemical interchange between both species is presented. It is shown that the one-way transition is governed by the formation of a multiple number of soluble oligomeric species consisting of varied stoichiometric ratios of both characterized homonuclear complexes.
通过四价铀阳离子与（1,4,7,10-四氮杂环十二烷-1,4,7,10-四（亚甲基膦酸））（DOTP）大环配体之间的相互作用，合成了两种新的铀的水配合物。鉴定出两种不同的同核配合物；第一种通过X射线晶体学表征为独特的“笼外”[U(DOTPH)]配合物，其中U阳离子以四方反棱柱几何构型与每个配体的4个膦酸臂八配位，具有C对称性。第二种是“笼内”[U(DOTPH)]配合物，其中四价阳离子位于大环的O和N平面之间。借助紫外可见吸收、H/P NMR、ATR-IR和MALDI-TOFMS分析技术，展示了这两种物种之间的化学交换。结果表明，单向转变受多种由两种表征的同核配合物的不同化学计量比组成的可溶性低聚物种的形成控制。
