Highly effective route to Si-O-Si moieties via O-silylation of silanols and POSS silanols with disilazanes: new tricks for an old dog.

A simple and highly practical catalyst-free O-silylation of silanols with commercially available disilazanes has been developed under mild conditions. In the case of POSS silanols and some silanols, it is necessary to use catalytic amounts of inexpensive bismuth(III) triflate as additional catalyst. This efficient chlorine-free protocol involves the synthesis of a wide range of important organosilicon derivatives such as unsymmetrical disiloxanes and functionalized silsesquioxanes.