Silane coordination polymerization

Tilley TD (1993) The coordination polymerization of silanes to poiysiianes by a o-bond metathesis mechanism. Implications for linear chain growth. Acc Chem Res 26(l) 22-29... 

T. D. Tilley, Acc. Chem. Res., 26, 22 (1993). The Coordination Polymerization of Silanes to Polysilanes by a cr-Bond Metathesis Mechanism. Implications for Linear Chain Growth. 

A second class of catalysts was discovered by Harrod and coworkers [8], who showed that titanocene and zirconocene derivatives dehydrogenate primary silanes (RSiH3) to poly silanes with 10-20 monomer units, in high yield. These catalysts therefore appear to be more promising with respect to production of polymers, and have revived interest in coordination polymerization routes to polysilanes. 

Investigations of silicon-metal systems are of fundamental interest, since stable coordination compounds with low valent silicon are still rare [64], and furthermore, silicon transition-metal complexes have a high potential for technical applications. For instance, coordination compounds of Ti, Zr, and Hf are effective catalysts for the polymerization of silanes to oligomeric chain-silanes. The mechanism of this polymerization reaction has not yet been fully elucidated, but silylene complexes as intermediates have been the subject of discussion. Polysilanes find wide use in important applications, e.g., as preceramics [65-67] or as photoresists [68-83],... 

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