The molecular and electronic structure of monomeric ([Fe(S2C2H2)(2)](z), [Fe(S2C2(C6H4-p-OCH3)(2))(2)](z)) and dimeric ([{Fe(S2C2H2)(2))(2)](z), iron bis(dithiolene) complexes, and of their phosphine adducts ([(PH3)Fe(S2C2H2)(2)](z), [(P(C6H5)(3))Fe(S2C2H2)(2)](z), [(PH3)Fe(S2C2(C6H4-p-OCH3)(2))(2)](z), carrying various charges (z = 0, 1 -, 2-), have been investigated by density functional theory (DFT). Net total spin polarization values S of zero, two, and four have been considered for all neutral model compounds and their dianions, whereas all monoanions have been examined with net total spin polarization values S of one, three, and five. The DFT calculations utilized the pure functional BP86, as well as the hybrid functionals B3LYP and B3LYP*. For the monomers, the calculations reveal the presence of redox non-innocent dithiolene ligands and antiferromagnetic coupling between the ligands and the metal center. For the dimers, complexes with antiferromagnetically coupled iron centers have been found to represent structures of low energy, if not lowest energy structures. The spin-coupling constant of [{Fe(S2C2H2)(2)}(2)](2-) is calculated as J = -230 cm(-1). On the basis of the computational results, a model for reversible, electrochemically controlled binding and release of phosphine ligands to iron bis(dithiolene) complexes is proposed. Only BP86 and B3LYP* results, but not those of B3LYP calculations, are in qualitative agreement with experimental findings. BP86 calculations provide the best quantitative match in comparison with the experiment.