Addition of aliphatic polyols to aqueous silicate solutions is shown to yield high concentrations of stable polyolate complexes containing five- or six-coordinated silicon. Coordinating polyols require at least four hydroxy groups, two of which must be in threo configuration, and coordinate to silicon via hydroxy oxygens at chain positions on either side of the threo pair. The remarkable ease by which these simple sugar-like molecules react to form hypervalent silicon complexes in aqueous solution supports a long-standing supposition that such species play a significant role in the biological uptake and transport of silicon and in mineral diagenesis.

No abstract

Two novel silicate anions, a singly-substituted cubic octamer (double four-ring cage with a pendant orthosilicate group) and its dimeric counterpart (two octameric cages linked by a single siloxane bridge), are detected by 29 Si NMR spectroscopy in concentrated tetraalkylammonium silicate solutions at the low alkalinity and high SiO 2 concentration typical of zeolite synthesis slurries.

Addition of cis-1,2-dihydroxycyclopentane to aqueous alkaline silicate solutions results in the spontaneous formation of three organosilicate species, each with a 2:1 ligand to Si ratio and a pentacoordinated silicon centre. By using a mixture of both cis-1,2-dihydroxycyclopentane and 1,4-anhydroerythritol we show unambiguously that all three species are diastereomers of the monomeric bis(diolato)-hydroxo complex, [(L=)(2)SiOH](-)(where L represents the cis-diol ligand), thus clarifying the general assignment of (29)Si NMR spectra reported for silicate solutions containing furanoidic sugars with vicinal cis-diol functionality, such as ribose.

Silicon-29 NMR spectra of a neutral, dilute aqueous silicic acid solution, with a pH and Si concentration typical of soil solutions, reveal that a significant fraction of the silicon is incorporated in two five-coordinated organosilicon complexes when sodium gluconate is present.