Metal dithiolene complexes are attractive for the development of novel materials with extended electronic properties. The preparation of Cp*Mo(dmit)(2)(-) and its investigation by cyclic voltammetry, antiferromagnetic resonance, and electron paramagnetic resonance are described. Complexes of this class, i.e., with heteroatom substitution on the dmit dithiolene ligand, are shown to exhibit conformational flexibility directly related to the orbital occupancy.