The first cationic Fe silyldiazenido complexes, [Fe(PP)2(NN–SiMe3)]+[BArF4]− (PP = dmpe/depe), have been synthesised and thoroughly characterised. Computational studies show the compounds to be useful structural and electronic surrogates for the more elusive [Fe(PP)2(NN–H)]+, which are postulated intermediates in the H+/e− mediated fixation of N2 by Fe(PP)2(N2) species