Formation and hydrolysis of gas-phase [UO₂ (R)]⁺ : R═CH₃ , CH₂ CH₃ , CH═CH₂ , and C₆ H₅

The goals of the present study were (a) to create positively charged organo-uranyl complexes with general formula [UO₂ (R)]⁺ (eg, R═CH₃ and CH₂ CH₃ ) by decarboxylation of [UO₂ (O₂ C─R)]⁺ precursors and (b) to identify the pathways by which the complexes, if formed, dissociate by collisional activation or otherwise react when exposed to gas-phase H₂ O. Collision-induced dissociation (CID) of both [UO₂ (O₂ C─CH₃ )]⁺ and [UO₂ (O₂ C─CH₂ CH₃ )]⁺ causes H⁺ transfer and elimination of a ketene to leave [UO₂ (OH)]⁺ . However, CID of the alkoxides [UO₂ (OCH₂ CH₃ )]⁺ and [UO₂ (OCH₂ CH₂ CH₃ )]⁺ produced [UO₂ (CH₃ )]⁺ and [UO₂ (CH₂ CH₃ )]⁺ , respectively. Isolation of [UO₂ (CH₃ )]⁺ and [UO₂ (CH₂ CH₃ )]⁺ for reaction with H₂ O caused formation of [UO₂ (H₂ O)]⁺ by elimination of ·CH₃ and ·CH₂ CH₃ : Hydrolysis was not observed. CID of the acrylate and benzoate versions of the complexes, [UO₂ (O₂ C─CH═CH₂ )]⁺ and [UO₂ (O₂ C─C₆ H₅ )]⁺ , caused decarboxylation to leave [UO₂ (CH═CH₂ )]⁺ and [UO₂ (C₆ H₅ )]⁺ , respectively. These organometallic species do react with H₂ O to produce [UO₂ (OH)]⁺ , and loss of the respective radicals to leave [UO₂ (H₂ O)]⁺ was not detected. Density functional theory calculations suggest that formation of [UO₂ (OH)]⁺ , rather than the hydrated U^V O₂ ⁺ , cation is energetically favored regardless of the precursor ion. However, for the [UO₂ (CH₃ )]⁺ and [UO₂ (CH₂ CH₃ )]⁺ precursors, the transition state energy for proton transfer to generate [UO₂ (OH)]⁺ and the associated neutral alkanes is higher than the path involving direct elimination of the organic neutral to form [UO₂ (H₂ O)]⁺ . The situation is reversed for the [UO₂ (CH═CH₂ )]⁺ and [UO₂ (C₆ H₅ )]⁺ precursors: The transition state for proton transfer is lower than the energy required for creation of [UO₂ (H₂ O)]⁺ by elimination of CH═CH₂ or C₆ H₅ radical.