Triorganophosphites containing substituents with different electronic and steric properties have been synthesized and tested as inhibitors of Karstedt's catalyst (complex Pt(0) with divinyltetramethyldisiloxane) in cross-linking of silicones via hydrosilylation. Relatively bulky or electron-withdrawing substituents in phosphite appeared to be the most efficient inhibitors of hydrosilylation showing sufficiently long pot-life at room temperature and short curing time at high temperature. New molecular complexes of Pt(DVTMDS)-selected phosphites have been synthesized and characterized. The new complexes proved to be effective catalysts of the curing process. The free phosphites as well as the phosphite-Pt complexes have been found resistant to oxidation and hydrolysis. (C) 2009 Elsevier B.V. All rights reserved.