Utility of a redox-active pyridine(diimine) chelate in facilitating two electron oxidative addition chemistry at uranium

Exposure of the uranium(IV) complex, Cp^PU(^MesPDI^Me) (1) (^MesPDI^Me = 2,6-((Mes)NCMe)₂–C₅H₃N; Mes = 2,4,6-trimethylphenyl; Cp^P = 1-(7,7-dimethylbenzyl)cyclopentadienyl), which contains a [^MesPDI^Me]³⁻ chelate, to I₂, Cl₂, PhSeCl, and PhEEPh (E = S, Se, Te) results in oxidative addition to form the uranium(IV) family, Cp^PU(XX′)(^MesPDI^Me) (X = X′ = I, Cl, EPh; X = SePh, X′ = Cl). Spectroscopic and structural studies support products with [^MesPDI^Me]¹⁻, indicating the reducing equivalents derive from this redox-active chelate.