Synthesis of cationic zinc complexes from protonated diazadienes and ZnR2 (R = Et, N(SiMe3)2). The crystal structures of [PriDADH][H2N{B(C6F5)3}2], [{PriDADZn(μ-OH)}2][H2N{B(C6F5)3}2]2, and [Ph*DADZnN(SiMe3)2][H2N{B(C6F5)3}2]

Protonation of View the MathML source(MeCNC6H3Pr2i-2,6)2 (PriDAD) with [H(OEt2)2][H2N{B(C6F5)3}2] affords the immonium salt [PriDADH][H2N{B(C6F5)3}2] (1) which shows intra- and inter-ionic NH⋯F hydrogen bonding in the solid state. Protolysis of ZnEt2 with [PriDADH][H2N{B(C6F5)3}2] gives [(PriDAD)ZnEt][H2N{B(C6F5)3}2] as a reactive intermediate. Repeated recrystallizations allowed the isolation of the dimeric zinc hydroxo complex [{(PriDAD)Zn(μ-OH)}2][H2N{B(C6F5)3}2]2 (2) which shows asymmetric OH-bridges. The analogous reaction of [Ph*DADH][H2N{B(C6F5)3}2] [Ph*DAD = (MeCdouble bond; length as m-dashNC6H3Ph2-2,6)2 with ZnMe2 or M{N(SiMe3)2gives the three-coordinate Zn and Cd compounds [(Ph*DAD)ZnMe][H2N{B(C6F5)3}2] (5) and [(Ph*DAD)M–N(SiMe3)2][H2N{B(C6F5)3}2] (6, M = Zn; 7, M = Cd). The crystal structures of 1, 2 and 6 are reported.