The reaction of [X][Hfe(CO)4] (X = mainly PPh4, but also NEt4, K and Ph3PNPPh3) with chlorophosphines for the synthesis of low coordinated phosphorus complexes is reviewed. Diphosphene (-P=P-), phospha-alkene (-P=C<), phospha-allene (-P=C=C<), and phosphide (>P) iron complexes have been in particular obtained, and characterized by 31 P NMR, and by X-ray diffraction in several cases.