Organocatalytic living ring-opening polymerization of cyclic carbosiloxanes

(Chemical Equation Presented) An organocatalytic route to narrowly dispersed poly(carbosiloxanes) of predictable molecular weight and end group fidelity is described. N-Heterocyclic carbenes (NHC) and 1,5,7-triazabicyclo[4. 4.0]dec-5-ene (TBD) catalyze the ring opening of cyclic carbosiloxanes. The pKb of the catalyst is important in preventing adverse transetherification reactions and obtaining well-defined polymers. Mechanistic studies indicate that hydrogen bonding to TBD or the NHC activates alcohols or silanols for ring-opening reactions. © 2006 American Chemical Society.