Silicon‐29 NMR study of the formation of monomethoxysilicic acid in methanolic alkaline silicate solutions

Samadi‐Maybodi, Abdolraouf; Harris, Robin K.; Azizi, Seyed Naser; Kenwright, Alan M.

doi:10.1002/mrc.868

Cited by 9 publications

(3 citation statements)

References 9 publications

(4 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Aliphatic alcohols and polyols have been reported to form small amounts of tetracoordinated species with tetrabutylammonium silicate at pH 12-12.5. 15,16 Under our conditions, such materials do react but form insoluble gels that give no 29 Si resonances. Our objectives were to characterize major, soluble products.…”

Section: Discussionmentioning

confidence: 81%

See 1 more Smart Citation

Silicate Complexes of Sugars in Aqueous Solution

Lambert

Singer

et al. 2004

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Certain sugars react readily with basic silicic acid to form soluble 2/1 (sugar/silicic acid) silicate complexes. Failure of monohydroxy compounds to give soluble products under these conditions indicates that the sugar silicates are chelates: five-membered diolato rings. Only furanose forms react. Pyranose sugars are stable under these conditions. Because all glycosides fail to react with silicic acid under these conditions, reaction appears to involve the anomeric position (C1 in aldoses, C2 in ketoses), which has a more acidic hydroxy group. Reaction is completed only when the anomeric hydroxy group is cis to an adjacent hydroxy group. The appropriate furanose form must have sufficient natural abundance and solubility to provide an observable product, as measured by (29)Si and (13)C NMR spectroscopy. These structural and practical constraints rationalize the successful reaction of the monosaccharides ribose, xylose, lyxose, talose, psicose, fructose, sorbose, and tagatose and the disaccharides lactulose, maltulose, and palatinose. Glucose, mannose, galactose, and sucrose, among others, failed to form complexes. This high selectivity for formation of sugar silicates may have ramifications in prebiotic chemistry.

show abstract

Section: Discussionmentioning

confidence: 81%

“…They do not, however, explain several observations, so that exceptions must be possible. Harris, 16 Kinrade, 15 and their respective co-workers found that methanol reacts with an ammonium silicate to form CH 3 OSi(OH) 3 . Methanol provides neither chelation nor heightened acidity.…”

Section: Discussionmentioning

confidence: 99%

Silicate Complexes of Sugars in Aqueous Solution

Lambert

Singer

et al. 2004

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Silicon-29-NMR spectroscopy has proved to be a valuable tool for obtaining information about the molecular structures, but isotopic enrichment in 29 Si NMR has generally been necessary in order to make diagnostic use of splitting patterns caused by 29 Si-29 Si scalar (J) coupling. About 25 anion structures have been proposed by using one and two dimension homonuclear NMR methods including COSY, TOCSY and NOESY [13][14][15][16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Structure‐Directing Effect of Surfactants on the Distribution of Silicate Species Using ²⁹Si‐NMR Spectroscopy

Samadi‐Maybodi

Goudarzi

Kirby

et al. 2008

J Surfact & Detergents

Self Cite

View full text Add to dashboard Cite

Silicate anions were studied using 29 Si NMR to investigate the structure-directing effect of a surfactant (sodium dodecylsulfate-SDS) on the distribution of silicate species present in alkaline silicate solutions. The distribution of the anions in the presence of polyelectrolytes was also investigated by 29 Si NMR through the use of different bases including tetramethyl ammonium hydroxide (TMAOH) and sodium hydroxide (NaOH). Both SDS and the polyelectrolytic solutions were shown to stabilize low molecular weight silicate species and thus inhibit polymerization.

show abstract

Silicon Chelation in Aqueous and Nonaqueous Media: The Furanoidic Diol Approach

Kästele

Klüfers

Kopp

et al. 2005

Chemistry A European J

View full text Add to dashboard Cite

Anhydroerythritol (AnEryt) shares some of its ligand properties with furanosides and furanoses. Its bonding to silicon centers of coordination number four, five, and six was studied by X-ray and NMR methods, and compared to silicon bonding of related compounds. Diphenyl(cycloalkylenedioxy)silanes show various degrees of oligomerization depending on the diol component involved. For example, Ph(2)Si(cis-ChxdH(-2)) (1) and Ph(2)Si[(R,R)-trans-ChxdH(-2))] (2; Chxd = cyclohexanediol) are dimeric, Ph(2)Si(AnErytH(-2)) (3) is monomeric, and Ph(2)Si(L-AnThreH(-2)) (4; AnThre = anhydrothreitol) is trimeric both in the solid state and in solution. Ph(2)Si(cis-CptdH(-2)) (5) (Cptd = cyclopentanediol) is monomeric in solution but dimerizes on crystallization. Si(AnErytH(-2))(2) (6) and Si(cis-CptdH(-2))(2) (7) are monomeric spiro compounds in solution but are pentacoordinate dimers in the crystalline state. Pentacoordinate silicate ions are found in A[Si(OH)(AnErytH(-2))(2)] (A = Na, 8 a; Rb, 8 b; Cs, 8 c). Related compounds are formed by substitution of the hydroxo by a phenyl ligand. K[SiPh(AnErytH(-2))(2)]1/2 MeOH (9) is a prototypical example as it shows the two most significant isomers in one crystal structure: the syn/anti and the anti/anti form (syn and anti define the oxolane ring orientation close to, or apart from, the monodentate ligand, respectively). syn/anti Isomerism generally rules the appearance of the NMR spectra of pentacoordinate silicates of furanos(id)e ligands. NMR spectroscopic data are presented for various pentacoordinate bis(diolato)silicates of adenosine, cytidine, methyl-beta-D-ribofuranoside, and ribose. In even more basic solutions, hexacoordinate silicates are enriched. Preliminary X-ray analyses are presented for Cs(2)[Si(CydH(-2))(3)] 21.5 H(2)O (10) and Cs(2)[Si(cis-InsH(-3))] cis-Ins8 H(2)O (11) (Cyd = cytidine, Ins = inositol).

show abstract

Silicon‐29 NMR study of the formation of monomethoxysilicic acid in methanolic alkaline silicate solutions

Cited by 9 publications

References 9 publications

Silicate Complexes of Sugars in Aqueous Solution

Silicate Complexes of Sugars in Aqueous Solution

Investigation of the Structure‐Directing Effect of Surfactants on the Distribution of Silicate Species Using ²⁹Si‐NMR Spectroscopy

Silicon Chelation in Aqueous and Nonaqueous Media: The Furanoidic Diol Approach

Contact Info

Product

Resources

About

Silicon‐29 NMR study of the formation of monomethoxysilicic acid in methanolic alkaline silicate solutions

Cited by 9 publications

References 9 publications

Silicate Complexes of Sugars in Aqueous Solution

Silicate Complexes of Sugars in Aqueous Solution

Investigation of the Structure‐Directing Effect of Surfactants on the Distribution of Silicate Species Using 29Si‐NMR Spectroscopy

Silicon Chelation in Aqueous and Nonaqueous Media: The Furanoidic Diol Approach

Contact Info

Product

Resources

About

Investigation of the Structure‐Directing Effect of Surfactants on the Distribution of Silicate Species Using ²⁹Si‐NMR Spectroscopy