Silylation of silicon bonded hydroxyl groups by silazanes and siloxanes containing an acetoxy group. N-trimethylsilylimidazole vs. dimethyldiacetoxysilane

► N-trimethylsilylimidazole (TMSIM) and dimethyldiacetoxysilane (DMDAS) for silylation. ► Calculation of minimum energy reaction paths for the silylation of silanol. ► TMSIM shows a very large activation barrier and a strong prereaction complex. ► DMDAS exhibits a relatively small activation barrier.