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The (chlorophosphine)iron tetracarbonyl complexes Me2NP(Cl)2Fe(CO)4, (Et2N)2P(Cl)Fe(CO)4, (¡'-Pr2N)2P(Cl)Fe(CO)4, [(Me3Si)2N]2P(Cl)Fe(CO)4, and (r-Bu)(Me2N)P(Cl)Fe(CO)4 have been prepared by reaction of the corresponding phosphorus(III) chlorides with Fe2(CO)9 in hexane solution. These Fe(CO)4 complexes have been characterized by elemental analysis and 31P NMR, 13C NMR, and IR spectroscopy. The coordinated phosphenium ions [(Me2N)P(Cl)Fe(CO)4]+, [(Et2N)2PFe(CO)4]+, [(/-Pr2N)2PFe(CO)4]+, [((Me3Si)2N)2PFe(CO)4]+, and [(i-Bu)(Me2N)PFe(CO)4]+ have been preparedas their AIC14~s alts by treatment of the respective precursor (chlorophosphine)iron tetracarbonyl complexes with the stoichiometric quantity of A12C16 in CH2C12 solution. These phosphenium ion complexes have been identified by elemental analysis and 31P NMR, 13C NMR, and IR spectroscopy. The -acceptor nature of phosphenium ion ligands is discussed on the basis of various spectroscopic data.