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

摘要

Exposure of the uraniumdv) complex, Cp~pU((~(Mes)PDI~(Me)) (1) ((~(Mes)PDI~(Me) = 2,6-((Mes)N=CMe)_2-C_5H_3N; Mes = 2,4,6-trimethylphenyl; Cp~p = 1-(7,7-dirnethylbenzyl)cyclopentadienyl), which contains a [(~(Mes)PDI~(Me)]~(3-) chelate, to I_2 Cl_2, PhSeCl, and PhEEPh (E = S, Se, Te) results in oxidative addition to form the uraniumdv) family, Cp~pU(XX')(~(Mes)PDI~(Me)) (X = X' = I, d EPh; X = SePh, X' = CD. Spectroscopic and structural studies support products with [~(Mes)PDI~(Me)]~(-1), indicating the reducing equivalents derive from this redox-active chelate.