Finely divided SiO2 dissolves in boiling methanol upon addition of the diphenol ligand 2 and excess sodium acetate along with sodium fluoride as catalyst. The sodium salt of 1, MSi, which contains hexacoordinated Si, is formed. The anion 1, MSi, is particularly stable. Thus, after 24 h in acetic acid at room temperature, its [HNEt3]⊕ salt is practically unchanged. The simple catechol complex decomposes completely under the same conditions.