Reaction pathways for the one- and two-electron reductions of [Fe(CN)(5)NO](2)(-) have been investigated by means of a density functional theory (DFT) approach combined with the polarized continuum model (PCM) of solvation. In addition, UV-vis spectroscopic data were obtained using ZINDO/S calculations including a point-charge model simulation of solvent effects. DFT methodologies have been used to assess the thermodynamical feasibility of protonation and cyanide-release processes for the reduced species. We conclude that [Fe(CN)(5)NO](3)(-) is a stable species in aqueous solution but may release cyanide yielding [Fe(CN)(4)NO](2)(-), consistent with experimental results. On the other hand, the [Fe(CN)(5)NO](4)(-) complex turns out to be unstable in solution, yielding the product of cyanide release, [Fe(CN)(4)NO](3)(-), and/or the protonated HNO complex. All the structural and spectroscopic (IR, UV-vis) predictions for the [Fe(CN)(5)HNO](3)(-) ion are consistent with the scarce but significant experimental evidence of its presence as an intermediate in nitrogen redox interconversion chemistry. Our computed data support an Fe(II)(LS) + NO(+) assignment for [Fe(CN)(5)NO](2)(-), an Fe(II)(LS) + NO assignment for the one-electron reduction product, but an Fe(I)(LS) + NO(+) for the one-electron product after dissociation of an axial cianide, and an Fe(II) + singlet NO(-) for the two-electron reduction species.