2.2.2-Cryptand complexes of neptunium() and plutonium()

• Published in: Chemical communications (Cambridge, England) England), 2022-01, Vol.58 (7), p.997-1
• Main Authors: 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
• Format: Article
• Language: English
• Subjects: Benzene; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Neptunium; Plutonium
• ISSN: 1359-7345; 1364-548X
• 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 2 ][I], obtained from the reaction between UI 3 and crypt, is treated with Me 3 SiOTf (OTf = O 3 SCF 3 ) 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 [AnI 3 (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 5f 3 U( iii ), 5f 4 Np( iii ), and 5f 5 Pu( iii ) electron configurations. The THF-soluble [An(crypt)(OTf) 2 ][OTf] complexes for An = Np and Pu were synthesized from AnI 3 (THF) 4 starting materials based on pilot studies of the An = U system. 5f 3 U( iii ), 5f 4 Np( iii ), and 5f 5 Pu( iii ) electron configurations are indicated by DFT analysis of their UV-visible-NIR spectra.