Direct formation of Ge-C bonds from GeO(2)

Germanium dioxide in the presence of 5% KOH reacted with dimethyl carbonate (DMC) at 250 degrees C to give (MeO)(4)Ge. The reaction of GeO(2) and DMC is similar to that reported for SiO(2); however, the rate of reaction for germanium is much higher than that of the corresponding silicon reaction. In a side-by-side experiment using SiO(2) and GeO(2) where the surface area of the silicon dioxide was 2 orders of magnitude higher than that of the GeO(2), the base-catalyzed reaction with DMC was about an order of magnitude higher for the germanium dioxide. When GeO(2) and 5% KOH were reacted with DMC at 350 degrees C, two products formed: (MeO)(4)Ge (70%) and MeGe(OMe)(3) (30%). Confirmation of the identity of MeGe(OMe)(3) was by GCMS, (1)H and (13)C NMR, and comparison to an authentic sample made by reaction of MeGeCl(3) with NaOMe. Experiments to determine the mechanism of the direct formation of Ge-C from GeO(2) ruled out participation from CO, H(2), or carbon. The KOH-catalyzed reaction of other metal oxides was explored including B(2)O(3), Ga(2)O(3), TiO(2), Sb(2)O(3), SnO(2), and SnO. Boron reacted to give unknown volatile products. Antimony reacted to give a solid which analyzed as Sb(OMe)(3). SnO reacted with DMC to give a mixture that included (MeO)(4)Sn and possibly Me(3)Sn(OMe).