Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis-Dioxo Fleeting Intermediate

Hartline D, Löffler S, Fehn D, Kasper JM, Heinemann FW, Yang P, Batista ER, Meyer K (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Book Volume: 145

Pages Range: 8927-8938

Journal Issue: 16

DOI: 10.1021/jacs.2c12868

Abstract

The activation of chalcogen-chalcogen bonds using organometallic uranium complexes has been well documented for S-S, Se-Se, and Te-Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O-O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O-O bond cleavage of 9,10-diphenylanthracene-9,10-endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [((^Me,AdArO)3N)U^III(dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [((^Me,AdArO)3N)U^V(DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. This uranium(V) bis-alkoxide can then be reduced with KC8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.

Authors with CRIS profile

Involved external institutions

Los Alamos National Laboratory United States (USA) (US)

How to cite

APA:

Hartline, D., Löffler, S., Fehn, D., Kasper, J.M., Heinemann, F.W., Yang, P.,... Meyer, K. (2023). Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis-Dioxo Fleeting Intermediate. Journal of the American Chemical Society, 145(16), 8927-8938. https://dx.doi.org/10.1021/jacs.2c12868

MLA:

Hartline, Douglas, et al. "Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis-Dioxo Fleeting Intermediate." Journal of the American Chemical Society 145.16 (2023): 8927-8938.

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