[Back]

D. Sturmayr, U. Schubert:
"DFT Calculations on the C-Cl/Si-H Exchange Catalyzed by P,N-Chelated Pt^II Complexes";
European Journal of Inorganic Chemistry, 13 (2004), 2658 - 2661.

The mechanism of the previously reported C-Cl/Si-H exchange reaction between H_xCCl_4-x (x = 0-3) and HSiMe₂Ph catalyzed by [PtMeCl(Ph₂PCH₂CH₂NMe₂-κ²P,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_xCCl_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.

http://aleph.ub.tuwien.ac.at/F?base=tuw01&func=find-c&ccl_term=AC04969146