Reaction of iPr2NPCl2with Na2Fe(CO)4gives the phosphorus-bridging carbonyl derivative (iPr2NP)2COFe2(CO)6or the triphosphine derivative (iPr2NP)3Fe2(CO)6as the major product depending upon whether the reaction is run in diethyl ether or tetrahydrofuran, respectively. Reaction of Et2NPCl2with Na2Fe(CO)4gives totally different types of products resulting from migration of diethylamino groups. The chemistry of these and related compounds is discussed.