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Synthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c12075· OSTI ID:2438924
 [1];  [1];  [2];  [1];  [2];  [1]
  1. Univ. of Kansas, Lawrence, KS (United States)
  2. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO22+. Here, in this work, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO22+ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E1/2) of –0.18 V vs Fc+/0 upon complexation, representing the most positive UVI/UV potential yet reported for the UO2n+ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U–Ooxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725; SC0019169
OSTI ID:
2438924
Alternate ID(s):
OSTI ID: 2447224
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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