DFT Calculations on the C−Cl/Si−H Exchange Catalyzed by P,N-Chelated PtII Complexes

✍ Scribed by Dietmar Sturmayr; Ulrich Schubert

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 114 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400029

✦ Synopsis

Abstract

The mechanism of the previously reported C−Cl/Si−H exchange reaction between H~x~CCl~4−~~x~ (x = 0−3) and HSiMe~2~Ph catalyzed by [PtMeCl(Ph~2~PCH~2~CH~2~NMe~2~‐κ^2^P,N)] [PtMeCl(P∩N)] was investigated by DFT calculations. The energetically less‐favored isomer of [PtMeCl(P∩N)], with Cl and P being cis, was identified to be the actual catalytic species. The catalytic reaction proceeds by oxidative addition of the silane, de‐coordination of the nitrogen atom of the P,N‐chelating ligand, reductive elimination of the chlorosilane and oxidative addition of the C−Cl bond of H~x~CCl~4−~~x~. The final step is the reductive elimination of the C−H bond with concomitant re‐coordination of the nitrogen atom of the P,N‐chelating ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)