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(mu-OH)}₂][H₂N{B(C₆F₅)₃}₂]₂, and [Ph*DADZnN(SiMe₃)₂][H₂N{B(C₆F₅)₃}₂]

Protonation of (MeC=NC6H3Pr2i-2,6)(2) (Pr'DAD) with [H(OEt2)(2)][HN{B(C6F5)(3)}(2)] affords the immonium salt [Pri- DADH][H2N{B(C6F5)(3)}(2)] (1) which shows intra- and inter-ionic NH center dot center dot center dot F hydrogen bonding in the solid state. Protolysis of ZnEt2 with [Pr(i)DADH][H2N{B(C6F5)(3)}(2)] gives [(Pr(i)DAD)ZnEt][H2N{B(C6F5)(3)}(2)] as a reactive intermediate. Repeated recrystallizations allowed the isolation of the dimeric zinc hydroxo complex [{(Pr(i)DAD)Zn(mu-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 = (MeC=NC6H3Ph2-2,6)(2) with ZnMe2 or M{N(SiMe3)(2) gives the three-coordinate Zn and Cd compounds [(Ph*DAD)ZnMe][H2N{B(C6F5)(3)}(2)] (5) and [(Ph*DAD)MN(SiMe3)(2)][H2N{B(C6F5)(3)}(2)] (6 M = Zn; 7, M = Cd). The crystal structures of 1, 2 and 6 are reported. (c) 2004 Elsevier B.V. All rights reserved.