Previously, the reactions of three μ-η²:η²-disulfidodicopper(II) complexes with N-alkylated cis,cis-1,3,5-triaminocyclohexane derivatives, [Cu₂(S₂)(R₃TACH)]X₂ [(R, X) = (Et, CF₃SO₃) (1), (iBu, SbF₆) (2), and (Bn, SbF₆) (3)], with PPh₃ and BnBr were reported. In order to clarify the relationship between the structures and reactivities, DFT calculations of the two complexes with bent and planar Cu₂S₂ structures have been performed, and the bond orders around the metals and atomic charges on Cu and S atoms have been estimated. The electron density is localized on Cu and S atoms when the dihedral angle (δ) is decreased; 1.137 and －0.470 for the bent type structure (δ = 156.67 °) and 1.107 and －0.450 for the planar one (δ = 175.56 °), respectively. The reactivity of disulfidodicopper(II) complexes against PPh₃ has been explained to depend upon the electrophilicity of Cu atoms and the nucleophilicity of S atoms, which are raised up by bending of two CuS₂ planes. These findings show that the disulfides of 1, 2, and 3 are electrophilic against exogenous substrates.