2.2.2-Cryptand complexes of neptunium(iii) and plutonium(iii)
2022
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.
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)I₂][I], obtained from the reaction between UI₃ and crypt, is treated with Me₃SiOTf (OTf = O₃SCF₃) in benzene to form the [U(crypt)(OTf)₂][OTf] complex. Similarly, the isomorphous Np(iii) and Pu(iii) complexes were obtained similarly starting from [AnI₃(THF)₄]. 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 5f³ U(iii), 5f⁴ Np(iii), and 5f⁵ Pu(iii) electron configurations.
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