2.2.2-镎（III）和钚（III）的穴状配体配合物。
2.2.2-Cryptand complexes of neptunium(III) and plutonium(III).
作者信息
Goodwin Conrad A P, Ciccone Sierra R, Bekoe Samuel, Majumdar Sourav, Scott Brian L, Ziller Joseph W, Gaunt Andrew J, Furche Filipp, Evans William J
机构信息
Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
Department of Chemistry, University of California Irvine, Irvine, CA 92697-2025, USA.
出版信息
Chem Commun (Camb). 2022 Jan 20;58(7):997-1000. doi: 10.1039/d1cc05904a.
New coordination environments are reported for Np(III) and Pu(III) based on pilot studies of U(III) in 2.2.2-cryptand (crypt). The U(III)-in-crypt complex, [U(crypt)I][I], obtained from the reaction between UI and crypt, is treated with MeSiOTf (OTf = OSCF) in benzene to form the [U(crypt)(OTf)][OTf] complex. Similarly, the isomorphous Np(III) and Pu(III) complexes were obtained similarly starting from [AnI(THF)]. All three complexes (1-An; An = U, Np, Pu) contain an encapsulated actinide in a THF-soluble complex. Absorption spectroscopy and DFT calculations are consistent with 5f U(III), 5f Np(III), and 5f Pu(III) electron configurations.
基于对2.2.2-穴醚（crypt）中U(III)的初步研究，报道了Np(III)和Pu(III)的新配位环境。由UI与穴醚反应得到的穴醚包合U(III)的配合物[U(crypt)I][I]，在苯中用MeSiOTf（OTf = OSCF₃）处理，形成[U(crypt)(OTf)][OTf]配合物。类似地，从[AnI(THF)₄]出发，以类似方式得到了同构的Np(III)和Pu(III)配合物。所有三种配合物（1-An；An = U、Np、Pu）在一种可溶于四氢呋喃的配合物中都含有一个被包封的锕系元素。吸收光谱和密度泛函理论计算结果与5f U(III)、5f Np(III)和5f Pu(III)的电子构型一致。
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