Exploiting catalytic dehydrogenative coupling in the synthesis and study of polysilanes

A reinvestigation of the catalytic activity of Wilkinson's catalyst, (Ph₃P)₃RhCl ( 1 ), for the dehydrogenative coupling reactions of secondary silanes has pointed the way toward the synthesis of key oligosilane reagents for structure property correlation studies of polysilanes. Implications are discussed for understanding the mechanisms of coupling and redistribution reactions of silanes mediated by such late metal centres. Also described are attempts to derivatize Si-H bonds in the resulting oligosilanes, which is highly relevant to the development of improved methods for the post-polymerization functionalization of polysilanes containing Si-H bonds.