A Homologous Series of Homoleptic Zinc Bis(1,4-di-tert-butyl-1,4-diaza-1,3-butadiene) 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).

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-tert-butylimidazolium triflate. Crystal data: dicationic 2 ([Zn(t-BuNCHCHN-t-Bu)(2)](OTf)(2), C(22)H(40)F(6)S(2)N(4)O(6)Zn), monoclinic, space group C2/c, with a = 18.015(6) Å, b = 9.257(6) Å, c = 20.012(5) Å, beta = 109.63(3) degrees, and Z = 4; monocationic 3.thf ([Zn(t-BuNCHCHN-t-Bu)(2)]OTf.thf, C(25)H(48)F(3)N(4)O(3)SZn), orthorhombic, space group P2(1)2(1)2(1), with a = 10.3077(6) Å, b = 17.1974(6) Å, c = 17.8241(13) Å, and Z = 4; monoanionic 5.thf (K(thf)(3)[Zn(t-BuNCHCHN-t-Bu)(2)], C(36)H(72)KN(4)O(3)Zn), triclinic, space group P&onemacr;, with a = 10.8702(10) Å, b = 11.5175(9) Å, c = 18.2815(13) Å, alpha = 73.795(6) degrees, beta = 74.227(6) degrees, gamma = 75.736(7) degrees, and Z = 2; 7 (1,3-di-tert-butylimidazolium triflate, C(12)H(21)F(3)N(2)O(3)S), orthorhombic, space group Pbca, with a = 14.4086(8) Å, b = 12.0293(8) Å, c = 18.6985(12) Å, and Z = 8.