Dinitrogen Activation, Partial Reduction, and Formation of Coordinated Imide Promoted by a Chromium Diiminepyridine Complex

Reduction of {2,6-[2,6-(i-Pr)2PhNC(CH3)]2(C5H3N)}CrCl (3) with NaH afforded the dinuclear dinitrogen complex {[{2,6-[2,6-(i-Pr)2PhNC(CH3)]2(C5H3N)}Cr(THF)]2(μ-N2)}·THF (5). Reaction carried in exclusion of dinitrogen afforded instead deprotonation of the ligand with the formation of {2-[2,6-(i-Pr)2PhNC(CH3)]-6-[2,6-(i-Pr)2PhNCCH2](C5H3N)}Cr(THF) (4). Further reduction of 5 with NaH yielded a curious dinuclear compound formulated as [{2,6-[2,6-(i-Pr)2PhNC(CH3)]2(C5H3N)}Cr(THF)][{2-[2,6-(i-Pr)2PhNC(CH3)]-6-[2,6-(i-Pr)2PhNCCH2](C5H3N)}Cr(THF)](μ-N2 H)(μ-Na)2 (6) containing two sodium atoms only bound to the dinitrogen unit and the π systems of the two diiminepyridine ligands. Subsequent reduction with NaH triggered a complex series of events, leading to the formation of a species formulated as {2-[2,6-(i-Pr)2PhNC(CH3)]-6-[2,6-(i-Pr)2PhNCCH2](C5H3N)}Cr(μ-NH)][Na(THF)] (7) on the basis of crystallographic, spectroscopic, isotopic labeling, and chemical degradation experiments.