This review commences with a survey of the general synthetic routes leading to aminophosphines containing the P-NH subgroup. Recent examples involving functionalised and chiral aminophosphines are included. The synthesis and structural properties of deprotonated aminophosphines, namely the phosphinoamides, are then described in detail. The reaction of phosphinoamides with main group elements/compounds and transition metal and lanthanide complexes, leading to the formation of inorganic chains, rings and phosphinoamido complexes is then discussed. The application of phosphinoamido complexes in olefin polymerisation catalysis is also covered. (c) 2005 Elsevier B.V. All rights reserved.