400091-98-7Relevant academic research and scientific papers
Dehydrogenative oligomerization of PhSiH3 catalyzed by (1-Me-Indenyl)Ni(PR3)(Me)
Fontaine, Frédéric-Georges,Zargarian, Davit
, p. 401 - 408 (2002)
The complexes (1-Me-Ind)Ni(PR3)Me (Ind = indenyl; R = Ph, 1; Cy, 2; Me, 3) can act as single-component precatalysts for the dehydrogenative oligomerization of PhSiH3 to (PhSiH)n with Mw up to 1.6 × 103 in the case of 3. The catalytic Si-Si bond formation is initiated by a second-order, concerted reaction between the Ni-Me precursor and PhSiH3 which releases CH4. Kinetic studies of this Si-H bond activation step gave the following activation parameters for the reaction of 3 with PhSiH3: ΔH? = 10.7 ± 0.7 kcal·mol-1; ΔS? = -42 = 2 eu; kH/kn (for reaction with PhSiD3 at 313 K) = 9.8 ± 0.5. The Ni-SiPhH2 species presumed to form in this reaction was not detected directly, but the presence of 1-SiPhH2-3-Me-Ind in the reaction mixtures, coupled with the fact that Ni(PMe3)4 is an active precatalyst for the oligomerization of PhSiH3, suggests that the silyl intermediate undergoes a reductive elimination to generate Ni(0) species which might be involved in the catalysis.
