The syntheses of cationic nickel complexes using N,N'-dimethyl piperazine 2,3-dithione (Me(2)Dt(0)) and N,N'-diisopropyl piperazine 2,3-dithione ((i)Pr(2)Dt(0)) ligands are reported. These ligands were used in synthesizing bis and tris(dithione)Ni(II) complexes as tetrafluoroborate or hexafluorophosphate salts, i.e., [Ni((i)Pr(2)Dt)(2)][BBO2 ([1a] [BF4](2)), [Ni(1Pr(2)Dt)(2)][PF6](2) Oa] [PF6](2)), [Ni(Me(2)Dt)] I-BF 4, 1 2 [ib] [BF4](2)), [Ni(iPr(2)Dt)3] [BF4](2) ([2a] [BF4](2)), and (Pr(2)Dt)(3)][PF6](2) ([2a] [PF6](2)), respectively. Complex [2a][PF6](2) was isolated from a methanolic solution of [la] [PF6](2). Compound [la] [BF4](2) crystallizes in a trigonal crystal system (space group, P31/c) and exhibits unique packing features, whereas [2a] [BF4](2) crystallizes in a monoclinic (P21/n) space group. Cyclic voltammograms of [1a][BF4], and [1b][BF4], are indicative of four reduction processes associated with stepwise single-electron reduction of the ligands. Spectroelectrochemical experiments on [la] [BF4](2) exhibit an intervalence charge transfer (IVCT) transition as a spectroscopic signature of the mixed-valence [Ni(Pr(2)Dt)((i)Pr(2)Dt(0))]- species. Analysis of this IVCT band suggests that this ligand based mixed valence complex, [Ni(iPr(2)Dt)((i)Pr(2)Dti(0))]-, behaves more like a traditional class metal based mixed-valence complex. The density functional theory (DFT) and time dependent DFT calculations provide a theoretical framework for understanding the electronic structures and the nature of excited states of the target compounds that are consistent with their spectroscopic and redox properties. Vibrational spectra of [1a](2+) and [2a](2+) were investigated as discrete species in the gas phase using infrared multiple photon dissociation (IRMPD) spectroscopy.