The radical cation of the redox active ligand 3,4-dimethyl-3',4'-bis-(diphenylphosphino)-tetrathiafulvalene ( P2) has been chemically and electrochemically generated and studied by EPR spectroscopy. Consistent with DFT calculations, the observed hyperfine structure (septet due to the two methyl groups) indicates a strong delocalization of the unpaired electron on the central S₂C=CS₂ part of the tetrathiafulvalene (TTF) moiety and zero spin densities on the phosphine groups. In contrast with the ruthenium(0) carbonyl complexes of P2 whose one-electron oxidation directly leads to decomplexation and produces P2^•+, one-electron oxidation of [Fe( P2)(CO)₃] gives rise to the metal-centered oxidation species [Fe^(I)( P2)(CO)₃], characterized by a coupling with two ³¹P nuclei and a rather large g-anisotropy. The stability of this complex is however modest and, after some minutes, the species resulting from the scission of a P–Fe bond is detected. Moreover, in presence of free ligand, [Fe^(I)( P2)(CO)₃] reacts to give the complex [Fe^(I)( P2)₂(CO)] containing two TTF fragments. The two-electron oxidation of [Fe( P2)(CO)₃] leads to decomplexation and to the P2^•+ spectrum. Besides EPR spectroscopy, cyclic voltammetry as well as FTIR spectroelectrochemistry are used in order to explain the behaviour of [Fe( P2)(CO)₃] upon oxidation. This behaviour notably differs from that of the Ru(0) counterpart. This difference is tentatively rationalized on the basis of structural arguments.