Si-C bond cleavage by hydride complexes of rhodium and iridium: comparison of Si-C(sp(2)) and Si-C(sp(3)) activation.
Single Si-C(R) (R = Ph, Me, Et) bond activation in {o-(Ph(2)P)C(6)H(4)}(2)Si(Me)(R) induced by Rh(H)(CO)(PPh(3))(3) was developed. The efficiency of Si-C(R) bond breaking reactions increased at 60 °C in the order Si-C(Et) < Si-C(Me) < Si-C(Ph) and strongly depended on the reaction temperature. Elevating the reaction temperature promoted Si-C(Me) over Si-C(Ph) bond activation, demonstrating that Si-C(Me) cleavage is entropically favored but enthalpically unfavored in comparison with Si-C(Ph) bond cleavage.
Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto 3-3-138, Osaka 558-8585, Japan.
Hajime
H
Kameo
Sho
S
Ishii
Hiroshi
H
Nakazawa