Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction

Abstract

A gas-phase uranyl peroxide dimer supported by three 12-Crown-4 ether (12C4) ligands, [(UO2)2(O2)(12C4)3)] 2+ (A), was prepared by electrospray ionization. Density functional theory (DFT) indicates a structure with two terminal 12C4 and the third 12C4 bridging the uranium centers. Collision induced dissociation (CID) of A resulted in elimination of the bridging 12C4 to yield a uranyl peroxide dimer with two terminal donor ligands, [(12C4)(UO2)(O2)(UO2)(12C4)] 2+ (B). Remarkably, CID of B resulted in elimination of the bridging peroxide concomitant with reduction of U(VI) to U(V) in C, [(12C4)(UO2)(UO2)(12C4)] 2+. DFT indicates that in C there is direct interaction between the two UO2 + , which can thus be considered as a so-called cation-cation interaction (CCI). This formal CCI, induced by tetradentate 12C4 ligands, corresponds to destruction of the linear uranyl moieties and creation of bridging U-O-U oxo-bonds. Based on the structural rearrangement to achieve the structurally extreme CCI interaction, it is predicted to also be accessible for PaO2 + , but is less feasible for transuranic actinyls.

Relativistic Effects Stabilize the Planar Wheel-like Structure of Actinide-Doped Gold Clusters: An@Au7 (An = Th to Cm)

“…Following, the low-lying competitors within the energy range of 0–30 kcal/mol were further reoptimized and confirmed at the PBE0 level of theory in the Gaussian 09 software as well as the Stuttgart energy-consistent pseudopotentials, with 60-frozen-electron and available basis set ECP60MWB_SEG for uranium atoms , and the SDD basis sets , for the gold and tungsten atoms. This level of the PBE0/U/ECP60MWB_SEG has exhibited accuracy in predicting the relative energies and properties of actinide compounds . Very recently, Adeyiga et al examined density functional theory (DFT) results of actinide compounds using multiconfigurational DFT and CCSD­(T) methods, which justified the reliability of DFT for actinide chemistry.…”

Controlling Cation‐Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

“…[60][61][62][63][64][65][66][67] Examples of gas-phase contributions to uranium chemistry include oxo-exchange of uranyl with water, [68] a nitrosyl complex, [69] a peroxide dimer, [70] and an "extreme" CCI. [71] Stand-alone com-putational studies have assessed stabilities of elementary CCIs in gas-phase uranyl dimers. [72,73] In the present work, electrospray ionization (ESI) of solutions containing uranyl and dicarboxylates was employed to generate gas-phase uranyl coordination complexes for reactivity studies in a quadrupole ion trap mass spectrometer (QIT-MS).…”

“…[ 60–67 ] Examples of gas‐phase contributions to uranium chemistry include oxo‐exchange of uranyl with water, [ 68 ] a nitrosyl complex, [ 69 ] a peroxide dimer, [ 70 ] and an “extreme” CCI. [ 71 ] Stand‐alone computational studies have assessed stabilities of elementary CCIs in gas‐phase uranyl dimers. [ 72,73 ]…”

Intrinsic reactivity of [OUCH]+: Apparent synthesis of [OUS]+ by reaction with CS2

“…Several gas‐phase studies have shown that it is possible to activate the axial U=O bonds of UO 2 2+ using collision‐induced dissociation (CID), and either substitute or eliminate one or more “yl” oxo ligands 1–10 . For example, Gibson and coworkers demonstrated that CID of [UO 2 (N 3 )Cl 2 ] − generates [UO (NO)Cl 2 ] − by elimination of N 2 1 and that [UO 2 (NCO)Cl 2 ] − dissociates by elimination of CO 2 to create [UONCl 2 ] − 2 .…”

“…Several gas-phase studies have shown that it is possible to activate the axial U=O bonds of UO 2 2+ using collision-induced dissociation (CID), and either substitute or eliminate one or more "yl" oxo ligands. [1][2][3][4][5][6][7][8][9][10] For example, Gibson and coworkers demonstrated that CID of [UO 2 (N 3 )…”