Reductive silylation of a uranyl dibenzoylmethanate complex: an example of controlled uranyl oxo ligand cleavage

Oxo group protonation and silylation of pentavalent uranyl Pacman complexes.

Oxo Ligand Substitution in a Cationic Uranyl Complex: Synergistic Interaction of an Electrophile and a Reductant.

Reaction of [U(VI)O2(dppmo)2(OTf)][OTf] (dppmo = Ph2P(O)CH2P(O)Ph2) with 4 equiv of Ph3SiOTf and 2 equiv of Cp2Co generates the U(IV) complex U(IV)(OTf)4(dppmo)2 (1), as a yellow-green crystalline solid in 83% yield, along with Ph3SiOSiPh3 and [Cp2Co][OTf]. This reaction proceeds via a U(IV) silyloxide intermediate, [U(IV)(OSiPh3)(dppmo)2(OTf)2][OTf] (2), which we have isolated and structurally...

The effect of the equatorial environment on oxo-group silylation of the uranyl dication: a computational study.

A theoretical investigation of the reductive oxo-group silylation reaction of the uranyl dication held in a Pacman macrocylic environment has been carried out. The effect of the modeling of the Pacman ligand on the reaction profiles is found to be important, with the dipotassiation of a single oxo group identified as a key component in promoting the reaction between the Si-X and uranium-oxo bon...

Uranyl sequestration: synthesis and structural characterization of uranyl complexes with a tetradentate methylterephthalamide ligand.

Uranyl complexes of a bis(methylterephthalamide) ligand (LH(4)) have been synthesized and characterized by X-ray crystallography. The structure is an unexpected [Me(4)N](8)[L(UO(2))](4) tetramer, formed via coordination of the two MeTAM units of L to two uranyl moieties. Addition of KOH to the tetramer gave the corresponding monomeric uranyl methoxide species [Me(4)N]K(2)[LUO(2)(OMe)].

Theoretical investigation of uranyl dihydroxide: oxo ligand exchange, water catalysis, and vibrational spectra.

Density functional theory is employed to investigate uranyl dihydroxide, UO2(OH)2, isomerization reaction energy barriers, including those occurring via proton shuttles. The ground-state structure of a uranyl dihydroxide complex containing a uranyl moiety with a near 90 degrees O=U=O bond angle is reported for the first time. Furthermore, we predict the vibrational spectra of these compounds. S...