A group 4 metal nitrogen bond is inserted into the carbon-nitrogen double bond of N,N’ di-tert-butylcarbodiimide to afford dimeric metal complexes of molecular formula [κ2-{Me3C-NC(=NCMe3)CH2NMe}M(NMe2)2]2 [M=Zr (1); and Hf (2)] supported by the N,N′-di-tert-butyl-2-(methylamino)acetimidamide ligand. Metal-nitrogen mediated C-H bond activation α in the nitrogen atom leads to the formation of acetimidamide complexes. An analogous reaction with zirconium and hafnium tetrakis(amide) with di-tert-butylcarbodiimides under hydrous conditions leads to insertion of the [M(NMe2)2O]2 moiety into complexes 1 and 2 to form another class of complexes formulated as [κ2-{Me3CNC(=NCMe3)CH2N−Me}M(NMe2)2{M(μ-O)NMe2}2]2 (M=Zr (3), Hf (4). The molecular structures of complexes 1, 3, and 4 in their solid states are reported here. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim