Synthesis and Reactivity of Trivalent Tp*U(CH<sub>2</sub>Ph)<sub>2</sub>(THF): Insertion vs Oxidation at Low-Valent Uranium–Carbon Bonds
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The synthesis of a rare uranium(III) bis(benzyl), Tp*U(CH2Ph)2(THF) (2), was achieved by salt metathesis of Tp*UI2(THF)2 with 2 equiv of KCH2Ph at low temperature. This was characterized by 1H NMR, infrared, and electronic absorption spectroscopy as well as X-ray crystallography. Addition of benzophenone to 2 forms the uranium(IV) radical coupling product Tp*U(CH2Ph)2(OC(Ph)2CH2Ph) (3), whereas N3Mes produces the imido derivative Tp*U(NMes)(CH2Ph)(THF) (4). Adding a further 1 equiv of N3Mes to tetravalent 4 results in U–C insertion to form the U(IV) triazenido species Tp*U(NMes)[(CH2Ph)N3(Mes)-κ2N1,2](THF) (5). Compound 2 also reacts with the redox-active 4,6-di-tert-butyl-2-[(2,6-diisopropylphenyl)imino]quinone (DIPPiq) to form the oxidized amido(phenolate) Tp*U(CH2Ph)(DIPPap) (6).
