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

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