The influence of catalyst structure on the dehydropolymerization of phenylsilane

Redistribution/Dehydrocoupling of Endocrine n-<TEX>$Bu_3SnH$</TEX> to Polystannanes Catalyzed by Group 4 Metallocene Complexes

“…Harrod's recent discovery of a group 4 metallocene-catalyzed dehydropolymerization of hydrosilanes, paved the new way to synthesize polysilanes [5] . Great efforts have been made to improve the dehydropolymerization method [6][7][8][9][10][11] . By comparison, polystannane, a tin analogue of polysilane, has not been studied until quite recently because of its synthetic difficulties.…”

“…Subsequently, Corey and coworker also described the similar dehydrocatenation of n-Bu 2 SnH 2 catalyzed by the Cp 2 MCl 2 /n-BuLi (M = Zr, Hf) combination [14c] . The Cp 2 MCl 2 /Red-Al (M = Ti, Zr, Hf) combination catalyst and the M(CO) 6 (M = Cr, MO, W) catalyst have been developed in our laboratory for dehydrocatenation of hydrosilanes to polysilanes [11,15] . Trialkyltin compounds are well known endocrine disruptors or environmental hormones unlike trialkylsilane compounds [16] .…”

Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes

“…They found that group 4 metallocenes, namely dimethyltitanocene and –zirconocene, catalyze silicon-silicon bond formation of phenylsilane accompanied by the loss of hydrogen (Equation 1) [10,11,12,13,14,15,16,17,18,19,20,21]. …”

“…In the course of investigations concerning transition metal silyl compounds, Tilley and co-workers were able to establish σ-bond metathesis as a major mechanistic pathway of the dehydrocoupling reaction [17,22,23]. Corey et al introduced metallocene dichloride/butyl lithium as an efficient catalyst system [24].…”

Polysilanes and Other Silicon-Containing Polymers

“…Anionic polymerization of masked disilenes and strained cyclosilanes [18] 3. Catalytic dehydrogenation of organosilanes such as PhSiH 3 [19][20][21].…”