title: Formation and characterization of the uranyl-SO2 complex, UO2(CH3SO2)(SO2)-.
abstract: The uranyl-SO(2) adduct, UO(2)(CH(3)SO(2))(SO(2))(-), was prepared and characterized by mass spectrometric studies as well as by density functional theory. Collision induced dissociation of UO(2)(CH(3)SO(2))(2)(-) in an ion trap resulted in the formation of UO(2)(CH(3)SO(2))(SO(2))(-), which spontaneously reacted with O(2) to give UO(2)(CH(3)SO(2))(O(2))(-), with SO(2) released. The UO(2)(CH(3)SO(2))(SO(2))(-) complex is computed to have a triplet ground state at the B3LYP level, and the SO(2) ligand is coordinated to uranium through two oxygen atoms, similar to the coordination mode of SO(2) in its complexes with hard metals. On the basis of the calculated geometric parameters and vibrational frequencies of the SO(2) ligand, the UO(2)(CH(3)SO(2))(SO(2))(-) complex can be considered as a U(V)O(2)(+) cation coordinated by SO(2)(-) and CH(3)SO(2)(-) anions. The UO(2)(CH(3)SO(2))(O(2))(-) complex is computed to have a peroxo ligand, suggesting that U(V) in UO(2)(CH(3)SO(2))(SO(2))(-) is oxidized to the U(VI) state upon O(2) substitution for SO(2).
authors: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors: Yu
authors: Y
authors: Gong
authors: John K
authors: JK
authors: Gibson