Electrochemical oxidation of (C6H5)3Pdouble bond; length as m-dashN(C6H5) and (C6H5)3Pdouble bond; length as m-dashN(C6H5) leads to EPR spectra which reveal the dimeric structure of the resulting radical cation. In contrast to this behaviour, oxidation of bis-iminophosphorane leads to [(C6H5)3Pdouble bond; length as m-dashN(C6H4)N=P(C6H5)3]radical dot+: In these species the unpaired electron is delocalized on the N(C6H4)N moiety and the persistency of the radical depends upon the relative position of the two Pdouble bond; length as m-dashN bonds.