A Homologous Series of Homoleptic Zinc Bis(1,4-di-tert-butyl-1,4-diaza-1,3-butadiene) Complexes: Kx[Zn(t-BuNCHCHN-t-Bu)2], Zn(t-BuNCHCHN-t-Bu)2, and [Zn(t-BuNCHCHN-t-Bu)2](OTf)x (x = 1, 2)

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Abstract
A homologous series of mono- and dicationic, neutral, and mono- and dianionic zinc diazabutadiene complexes, Kx[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, C22H40F6S2N4O6Zn), monoclinic, space group C2/c, with a = 18.015(6) Å, b = 9.257(6) Å, c = 20.012(5) Å, β = 109.63(3)°, and Z = 4; monocationic 3·thf ([Zn(t-BuNCHCHN-t-Bu)2]OTf·thf, C25H48F3N4O3SZn), orthorhombic, space group P212121, 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], C36H72KN4O3Zn), triclinic, space group P1̄, with a = 10.8702(10) Å, b = 11.5175(9) Å, c = 18.2815(13) Å, α = 73.795(6)°, β = 74.227(6)°, γ = 75.736(7)°, and Z = 2; 7 (1,3-di-tert-butylimidazolium triflate, C12H21F3N2O3S), orthorhombic, space group Pbca, with a = 14.4086(8) Å, b = 12.0293(8) Å, c = 18.6985(12) Å, and Z = 8.

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