Ky. Blohowiak et al., SIO2 AS A STARTING MATERIAL FOR THE SYNTHESIS OF PENTACOORDINATE SILICON COMPLEXES .1., Chemistry of materials, 6(11), 1994, pp. 2177-2192
SiO2 as silica gel, fused silica, or quartzite will react readily in e
thylene glycol (EG) with 1 equiv of alkali (M) hydroxide (except Na) t
o produce, in essentially quantitative yield, monomeric pentacoordinat
e glycolato silicates [M(OCH2CH2O)2SiOCH2CH2OH] containing two bidenta
te glycol ligands and one monodentate ligand. On heating, one EG is lo
st per two monomer units forming dimeric species, [M2Si2(OCH2CH2O)5],
or polymers, [MSi(OCH2CH2O)2.5]x. The Na derivative precipitates out o
f solution as the dimer. In experiments run with fused silica, the dis
solution process exhibits a first-order dependence on base concentrati
on and silica surface area. The E(a) for silica dissolution is 14 +/-
2 kcal/mol with DELTAH(double dagger) almost-equal-to 11 kcal/mol and
DELTAS(double dagger) almost-equal-to - 44 cal/mol K. In the absence o
f base, the silica surface reacts with EG to form an alkoxy-modified s
urface as determined by diffuse reflectance FTIR spectroscopy (DRIFTS)
. In the presence of base, only hydroxyl groups are seen on the silica
surface. A mechanism for dissolution is proposed based on these obser
vations. The dissolution process appears to be relevant to the nonaque
ous synthesis of zeolites, especially silica-sodalite (ZSM-5), which a
re prepared under very similar conditions. The monomeric, anionic glyc
olato silicates exhibit trigonal-bipyramidal geometry, with no apparen
t contact interactions between the anionic framework and the alkali me
tal counterions. The monomers, dimers and polymers are characterized b
y chemical analysis, X-ray powder diffractometry, FTIR, solution and s
olid-state MAS Si-29 NMR, and thermal gravimetric analysis. The monome
rs dissolve readily in methanol but appear to do so via a ligand-excha
nge process wherein some of the glycolato ligands are displaced by met
hoxy ligands. On heating, the dimers/polymers decompose to phase-pure
alkali silicates.