Reaction of [PPN][HFe(CO)4] (PPN = bis(triphenylphosphine)iminium) with PCl3 in a 1:1 ratio produced small amounts of [PPN][P{Fe(CO)4}2Cl2] ([PPN][Ia]). Reaction of [Et4N][HFe(CO)4] with AsCl3 in a 1:0.75 ratio in THF at −78 °C produced [Et4N][As{Fe(CO)4}2Cl2] ([PPN][Ib]) as the majority product. The compound [PPN][(CO)4FePCl2O] ([PPN][II]) was obtained from the reaction of Fe2(CO)9 with PCl3 in THF. In contrast, [Et4N][HFe(CO)4] reacted with PCl3 at −78 °C in a 2:1 ratio to yield [Et4N][Fe2(CO)6{(μ4-PFe(CO)4)2(μ-CO)}{μ-PCl2}] ([Et4N][III]) as the majority product. The compounds were characterized spectroscopically and by single-crystal X-ray diffraction analyses.