Two new aminophosphines, benzyl-N(Ph2P)(2) and 2-picolyl-N(Ph2P)(2), have been synthesized. Oxidation of the aminophosphines with either hydrogen peroxide, elemental sulfur and selenium gave the corresponding oxides, sulfides and selenides benzyl-N(Ph2P=E)(2) and 2-picolyl-N(Ph2P=E)(2), where E = O, S, or Se. Complexes [benzyl-N(Ph2P)(2)]MCl2 and [2-picolyl-N(Ph2P)(2)]MCl2, where M = Pd, Pt, were obtained by the reaction of the aminophosphines with MCl2(cod). The new compounds were characterised by NMR, IR spectroscopy and microanalysis. Furthermore, representative solid-state structures of the palladium and platinum complexes were determined using single crystal X-ray diffraction analysis. The palladium complexes were further investigated as potential catalysts in C-C coupling reactions. (c) 2008 Elsevier B. V. All rights reserved.