Cationic silyldiazenido complexes of the Fe(diphosphine)2(N2) platform: structural and electronic models for an elusive first intermediate in N2 fixation

Abstract

The first cationic Fe silyldiazenido complexes, [Fe(PP)₂(NN–SiMe₃)]⁺[BAr^F₄]⁻ (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.