Unexpected Migratory Insertion Reactions of M(alkyl)₂ (M = Zn, Cd) and Diamidocarbenes

The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH₃ and P₄. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6-MesDAC-R)MR] (M = Zn, Cd; R = Et, Me; Mes = mesityl). These species were formed via the spectroscopically characterised intermediates, [(6-MesDAC)MR₂], exhibiting barriers to migratory insertion which increase in the order MR₂ = ZnEt₂ < ZnMe₂ < CdMe₂. Compound [(6-MesDAC-Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent beta-H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M-R, M-H).