SIO2 AS A STARTING MATERIAL FOR THE SYNTHESIS OF PENTACOORDINATE SILICON COMPLEXES .1.

Citation
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
Citations number
62
Categorie Soggetti
Chemistry Physical","Material Science
Journal title
ISSN journal
08974756
Volume
6
Issue
11
Year of publication
1994
Pages
2177 - 2192
Database
ISI
SICI code
0897-4756(1994)6:11<2177:SAASMF>2.0.ZU;2-1
Abstract
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.