Amide C−N Bond Cleavage and Formation of Nitride Promoted by a Niobium(II) Cluster

Reaction of the diamagnetic cluster (TMEDA) 2 Nb 2 Cl 5 Li(TMEDA) with the (3,5-Me 2 Ph)(Ad)NLi (Ad = adamantyl) amide led to a rare case of C−N bond activation and formation of tetravalent, dinuclear, and diamagnetic {(3,5-Me 2 Ph)(Ad)N]Nb(3,5-Me 2 Ph)} 2 (μ-NAd) 2 ·ether ( 1) containing a Nb−Nb single bond. Conversely, a similar reaction carried out with [Cy 2 NLi] 4 (Cy = cyclohexyl) yielded dinuclear {[(Cy 2 N) 2 Nb] 2 (μ-N)}(μ 3 -N)Li(TMEDA) ( 2 ).