Reported here are synthetic studies probing highly reduced iron centers in an encumbering tetraisocyano ligand environment. Treatment of FeCl2 with sodium amalgam in the presence of 2 equiv of the m-terphenyl isocyanide CNArMes2 (Ar-Mes2 = 2,6-(2,4,6-Me3C6H2)(2)C6H3) produces the disodium tetraisocyanoferrate Na2[Fe(CNArMes2)(4)]. Structural characterization of Na-2[Fe(CNArMes2)(4)] revealed a tight ion pair, with the Fe center adopting a tetrahedral coordination geometry consistent with a d(10) metal center. Attempts to disrupt the cationanion contacts in Na-2[Fe(CNArMes2)(4)] with cation-sequestration reagents lead to decomposition, except for the case of 18-crown-6, where a mononuclear complex featuring a dianionic 1-azabenz[b]azulene ligand was isolated in low yield. Formation of this 1-azabenz[b]azulene is rationalized to proceed by an aza-Buchner ring expansion of a CNArMes2 ligand mediated by a coordinatively unsaturated Fe center. Disodium tetraisocyanoferrate Na-2[Fe(CNArMes2)(4)] is readily protonated by trimethylsilanol (HOSiMe3) to produce the monohydride ferrate salt, Na[HFe(CNArMes2)(4)], the anionic portion of which serves as an isocyano analogue of the hydrido-tetracarbonyl metalate [HFe(CO)(4)](-). Treatment of Na[HFe(CNArMes(2))(4)] with methyl triflate (MeOTf; OTf = [O3SCF3](-)) at low temperature in the presence of dinitrogen yields the five-coordinate Fe(0) complex Fe(N-2)(CNArMes2)(4). The formation of Fe(N-2)(CNArMes2)(4) in this reaction is consistent with the intermediacy of the neutral tetraisocyanide Fe(CNArMes2)(4). The decomposition of Fe(N-2)(CNArMes2)(4) to the dimeric complex [Fe(eta(6)-(Mes)-mu(2)-C-CNArMes)](2) and a seven-membered cyclic imine derived from a CNArMes2 ligand is presented and provides insight into the ability of CNArMes2 and related m-terphenyl isocyanides to stabilize zerovalent four-coordinate iron complexes in a strongly p-acidic ligand field.