Abstract
The dehydrocoupling of hydrosilanes to polysilane products is promoted by the combination of a Group 4 metallocene dichloride with nBuLi. The effect of a trimethylsilyl Cp-substitutent on the rate and product distribution for the dehydrocoupling of PhRSiH2 (R = H, Me) has been examined for hafnium precursors. A slower rate of reaction is observed with (C5H4SiMe3)2 HfCl2-(1)/2nBuLi compared to (C5H5)2HfCl2/2nBuLi but the average molecular weight of the polysilane produced is of similar magnitude. Both rac(2)-and meso(3)-[Me2C(C5H3SiMe3)2]HfCl2 precatalysts convert PhSiH3 to polysilane products at a faster rate than does [Me2C(C5H4)2, but only oligomeric products are formed at room temperature. When dehydrocoupling reactions of PhSiH3 promoted by 2 and 3 are conducted above room temperature, loss of the Cp-based ligand is observed. The silylcyclopentadienyl hafnium systems are ineffective for the coupling of secondary silanes. The reaction of 1 and 2 with 2 equiv of nBuLi is rapid at room temperature to giv...
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