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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]3UIV(OCPhPh-CPh2O)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 chargeseparated 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)2K][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. [ABSTRACT FROM AUTHOR]

The complex [(nacnac)Ti(OAr)]2(μ2:η2,η2-P2) ( 1) is formed via reductive decarbonylation of the phosphaethynolate ion −[OCP], which serves as a P atom source. Complex 1 is the first structurally characterized Group 4 transition metal P2 complex and its structure reveals the rhombic Ti2P2 core is essentially planar with short bond lengths suggesting some degree of multiple bonding character between the Ti-P and P-P sites. Computational studies of 1 provide an understanding of the Ti2P2 core as well as the origin of the highly downfield 31P NMR spectroscopic signal. [ABSTRACT FROM AUTHOR]