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

Golwankar, Riddhi R.; Ervin, Alexander C.; Makoś, Małgorzata Z.; Mikeska, Emily R.; Glezakou, Vassiliki-Alexandra; Blakemore, James D.

doi:10.1021/jacs.3c12075

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

Journal Article · 28 March 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c12075 · OSTI ID:2438924

^[1]; Ervin, Alexander C. ^[1];

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Univ. of Kansas, Lawrence, KS (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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 (E_1/2) of –0.18 V vs Fc^+/0 upon complexation, representing the most positive U^VI/U^V 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–O_oxo 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.

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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:: AC05-00OR22725; SC0019169; AC02-05CH11231

OSTI ID:: 2438924

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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CCDC 2295456: Experimental Crystal Structure Determination Riddhi, Golwankar,; Alexander, Ervin,; Malgorzata, Makos, https://doi.org/10.5517/ccdc.csd.cc2h1lz4 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2295457: Experimental Crystal Structure Determination Riddhi, Golwankar,; Alexander, Ervin,; Malgorzata, Makos, https://doi.org/10.5517/ccdc.csd.cc2h1m06 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2295458: Experimental Crystal Structure Determination Riddhi, Golwankar,; Alexander, Ervin,; Malgorzata, Makos, https://doi.org/10.5517/ccdc.csd.cc2h1m17 The current record is supplemented by this dataset	dataset	January 2024

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

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