Twofold Insertion of Isocyanides into the GaGa Bond of Tetrakis[bis(trimethylsilyl)methyl]digallane(4)

Tetrakis[bis(trimethylsilyl)methyl]digallane(4) ( 1 ) reacts with tert ‐butyl or aryl=isocyanides [aryl = phenyl, o ‐methylphenyl, o ‐methoxyphenyl, p ‐methoxyphenyl) by a twofold insertion of the central carbon atoms into the Ga–Ga bond and formation of C–C single bonds. 1,4‐Diazabutadiene derivatives bound to two R 2 Ga groups are formed ( 2–6 ), which in contrast to an aluminium analog exhibit only weak interactions between the imine nitrogen atoms and the coordinatively unsaturated gallium atoms as indicated by NMR spectroscopy and the long Ga–N distances in the molecular structures of three products: 2 (R = C 6 H 5 ), 4 (R = o ‐MeOC 6 H 4 ), and 6 (R = CMe 3 ).