Base-stabilized silanone complex Cp*(OC)(2)W(SiMe3){O=SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe3)(=SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 degrees C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe3)} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 degrees C.