Applying novel and efficient method, new tris(triorganosilyl)phosphites were synthesized and further used for the preparation of new well-defined platinum complexes [Pt(DVTMDS){P(OSiR3)(3)}] (DVTMDS=(H2C=CHSiMe2)(2)O, R-3 =Si7O9((i)OCt)(7), Pr-i(3), MePh2, Ph-3, ((OBu)-Bu-t)(3), (OSiMe3)(3)) which were well characterized by spectroscopic methods. Structures of two platinum(0) complexes, [Pt{eta(4)(H2C=CHSiMe2)(2)O} {P(OSiPh3)(3)}] (10) and [Pt{eta(4)-(H2C=CHSiMe2)(2)O}{P(OSi((OBu3)-Bu-t)(3)}] (11) were determined by X-ray analysis. The new complexes proved to be very effective catalysts of a crosslinking of silicones via hydrosilylation at elevated temperature with relatively short cure time and the enthalpy of network formation similar to that of Pt-Karstedt's/DAM (DAM = diallyl maleate) catalytic system. Additionally, the catalyzed silicone formulation had sufficiently long pot-life at room temperature. (C) 2010 Elsevier B.V. All rights reserved.