A homologous series of mono-and dicationic, neutral, and mono-and dianionic zinc diazabutadiene complexes, K-x[Zn(t-BuNCHCHN-t-Bu)(2)], Zn(t-BuNCHCHN-t-Bu)(2), and [Zn(t-BuNCHCHN-t-Bu)(2)](OTf)(x) (x = 1, 2), have been prepared and isolated in pure form. The crystal structures of the mono-and dicationic as well as of the monoanionic complexes are reported. In this series, the formal charge on the t-BuNCHCHN-t-Bu ligands ranges from -2 to +2, and the way in which the molecular geometry of the ligands varies with the charge is discussed. [Zn(t-BuNCHCHN-t-Bu)(2)](OTf)(2), reacts with methanol to give 1,3-di-terr-butylimidazolium triflate. Crystal data : dicationic 2 ([Zn(t-BuNCHCHN-t-Bu)(2)](OTf)(2), C22H40F6S2N4O6Zn), monoclinic, space group C2/c, with a = 18.015(6) Angstrom, b = 9.257(6) Angstrom, c = 20.012(5) Angstrom, beta = 109.63(3)degrees, and Z = 4; monocationic 3 . thf ([Zn(t-BuNCHCHN-t-Bu)(2)]OTf . thf, C25H38F3N4O3SZn), orthorhombic, space group P2(1)2(1)2(1), with a = 10.3077(6) Angstrom, b = 17.1974(6) Angstrom, c = 17.8241(13) Angstrom, and Z = 4; monoanionic 5 . thf (K(thf)(3)[Zn(t-BuNCHCHN-t-Bu)(2)], C36H72KN4O3Zn), triclinic, space group P (1) over bar, with a = 10.8702(10) Angstrom, b = 11.5175(9) Angstrom, c = 18.2815(13) Angstrom, a 73.795(6)degrees, beta = 74.227(6)degrees, gamma = 75.736(7)degrees, and Z = 2; 7 (1,3-di-tert-butylimidazolium triflate, C12H21F3N2O3S),orthorhombic, space group Pbca, with a = 14.4086(8) Angstrom, b = 12.0293(8) Angstrom, c = 18.6985(12) Angstrom, and Z = 8.