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

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.