Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

Kumar, Amit; Lionetti, Davide; Day, Victor W.; Blakemore, James D.

doi:10.1021/jacs.9b11903

Title: Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

Journal Article · Mon Jan 13 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11903· OSTI ID:1600028

Kumar, Amit ^[1]; Lionetti, Davide ^[1]; Day, Victor W. ^[1];

^[1]

Univ. of Kansas, Lawrence, KS (United States)

Capture and activation of the water-soluble uranyl dication (UO₂²⁺) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO₂²⁺ is held in close proximity to a range of redox-inactive metals by a tailored macrocyclic ligand. Crystallographic and spectroscopic studies confirm assembly of homologous U^VI(μ-O_Ar)₂Mⁿ⁺ cores with a range of mono-, di-, and tri-valent Lewis acids (Mⁿ⁺). Cyclic voltammetry data demonstrate that the U^VI/U^V reduction potential in these com-plexes is modulated over a span of 600 mV, depending linearly on the Lewis acidity of the redox-inactive metal with a sensitivity of 61±9 mV/pK_a unit. These findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

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Research Organization:: Univ. of Kansas, Lawrence, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019169

OSTI ID:: 1600028

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 6; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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CCDC 1960631: Experimental Crystal Structure Determination Amit, Kumar,; Davide, Lionetti,; W., Day, Victor https://doi.org/10.5517/ccdc.csd.cc23t65b The current record is supplemented by this dataset	dataset	January 2020
CCDC 1960625: Experimental Crystal Structure Determination Amit, Kumar,; Davide, Lionetti,; W., Day, Victor https://doi.org/10.5517/ccdc.csd.cc23t5z3 The current record is supplemented by this dataset	dataset	January 2020
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Title: Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

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