Abstract
Methyl benzoate, N,N-dimethylbenzamide, and benzophenone were reduced by UIII [N(SiMe3 )2 ]3 resulting in uranium(IV) products. Reduction of benzophenone lead to UIV [OC⋅Ph2 )][N(SiMe3 )2 ]3 , (1.1) which forms the dinuclear complex, [N(SiMe3 )2 ]3 UIV (OCPhPh-CPh2 O)UIV [N(SiMe3 )2 ]3 (1.2), through coupling of the ketyl radical species upon crystallization. Reaction of N,N-dimethylbenzamide with UIII [N(SiMe3 )2 ]3 resulted in UIV [OC⋅(Ph)(NMe2 )][N(SiMe3 )2 ]3 (2), a uranium(IV) compound and the first example of a charge-separated amide radical. In the case of methyl benzoate, the reduction resulted in UIV (OMe)[N(SiMe3 )2 ]3 (3) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded UV (=NSiMe3 )[N(SiMe3 )2 ]3 . Additionally, 2 was reduced with potassium graphite resulting in [U(μ-O)[O=C(NMe2 )(Ph)][N(SiMe3 )2 ]2 ]2 (4), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15-crown-5 afforded isolation of the mono-oxo compound, [(15-crown-5)2 K][UO[N(SiMe3 )2 ]3 ] (5). The results expand the reduction capabilities of UIII complexes and demonstrate a strategy for isolating novel metal-stabilized radicals.
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