Assembly of metallo-macrocycles through reductive C-C coupling of alkylnitriles by an Mg-Mg-bonded compound

Low-valent metal complexes have attracted much research interest owing to their novel reactivities toward small molecules. Herein the reactivity of the α-diimine-ligated, Mg-Mg-bonded compound [K(THF)₃]₂[LMg-MgL] (1, L = [(2,6-iPr₂C₆H₃)NC(Me)]₂²⁻) with aliphatic nitriles has been studied. Complex 1 readily activates n-alkylnitriles RCuN; R = propyl, butyl, and pentyl) to afford the unique trinuclear magnesium metallo-macrocyclic complexes, [LMg(μ-{(NC-C(R)C(CH₂R)-NH})]₃[K₃(Solv)₆] (2-4: R = -(CH₂)_nCH₃, n = 2, 3, or 4; Solv = THF/DME), through a reductive deprotonation of the α-H of one nitrile molecule and C-C coupling between this α-carbon and the cyanide (CN) group of another nitrile, followed by a 1,3-H shift. The results demonstrate the possibility of assembling supramolecular architectures based on the α-diimine [LMg] fragment through small molecule activation.