The paper gives a short survey on the coordination properties of H-spirophosphoranes towards transition metals. The emphasis is on the application of H-spirophosphorane complexes in catalysis. Spirophosphoranes supported by transition metals, palladium or rhodium, have been identified as ligands in metal-catalysed enantioselective catalysis; connected to palladium centres, they exhibit catalytic properties in cross-coupling reactions. Rhenium complexes incorporating spirophosphoranes appear to act as excellent co-catalysts in oxidation reactions. It is demonstrated how fine tuning within the structure of phosphorus ligands can determine the catalytic properties of transition metal complexes. (c) 2012 Elsevier B.V. All rights reserved.