The acyclic diene metathesis (ADMET) polymerization approach to silicon containing materials

The utility of acyclic diene metathesis (ADMET) polymerization in the synthesis of silicon-carbon hybrid materials is reviewed. Silicon containing macromolecules are synthesized from organosilicon alpha,omega-dienes (except those which are divinyl substituted). As an extension of olefin metathesis, ADMET is catalyzed by many transition metal complexes which either initiate the formation of carbene complexes ("ill-defined" catalysts) or by metallacarbene complexes ("well-defined" catalysts). Constant developments of catalytic systems have made this methodology more viable by allowing incorporation of numerous silicon containing functionalities into the polymer's backbone or pendant to it. Divinyl substituted organosilicon derivatives are inert to ADMET conditions; they undergo silylative coupling (SC) polycondensation catalyzed by ruthenium and rhodium complexes yielding metathesis-like products, although this transformation proceeds via a non-metallacarbene mechanism. (c) 2006 Elsevier B.V. All rights reserved.