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Abstract Lanthanide triflates have been used to incorporate NdIIIand SmIIIions into the 2.2.2‐cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf)3complexes (Ln=Nd, Sm; OTf=SO3CF3) react with crypt in THF to form the THF‐soluble complexes [LnIII(crypt)(OTf)2][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these LnIII‐in‐crypt complexes using KC8in THF forms the neutral LnII‐in‐crypt triflate complexes [LnII(crypt)(OTf)2]. DFT calculations on [NdII(crypt)]2+], the first NdIIcryptand complex, assign a 4f4electron configuration to this ion.
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2.2.2-Cryptand complexes of neptunium( iii ) and plutonium( iii )
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.
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- Award ID(s):
- 1835909
- PAR ID:
- 10388393
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 58
- Issue:
- 7
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 997 to 1000
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1CC05904A
