Stable five- and six-coordinated silicate anions in aqueous solution

Science

Volumn 285, Issue 5433, 1999, Pages 1542-1545

  Kinrade, Stephen D ^a   Del Nin, Jeffrey W ^a   Schach, Andrew S ^a   Sloan, Todd A ^a   Wilson, Krista L ^a   Knight, Christopher T G ^b  

^a LAKEHEAD UNIVERSITY   (Canada)

^b UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; POLYOL; SILICATE;

ALKALINITY; AQUEOUS SOLUTION; ARTICLE; CHEMICAL BOND; COMPLEX FORMATION; ION TRANSPORT; IONIZATION; MOLECULAR MODEL; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PRIORITY JOURNAL; STRUCTURE ANALYSIS;

ANIONS; CHEMISTRY, PHYSICAL; HYDROGEN-ION CONCENTRATION; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; SILICATES; SILICON; SOLUTIONS; SUGAR ALCOHOLS; WATER;

EID: 0033520413     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.285.5433.1542     Document Type: Article

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23. o.
24. That is, only when there are two adjacent hydroxy groups occurring on opposite sides of the molecule's Fischer projection (Fig. 3).
25. 13C NMR signals corresponding to Si-coordination sites on the polyol shift up-frequency by 1 to 3 ppm from their bulk solution values. Thus, whereas free D-threitol resonates at 62.9 (C-1,4) and 71.8 ppm (C-2,3), the major threitol-Si complex resonates at 64.7, 64.9 (-OSi coordinated C-1,4), 70.7, and 71.7 ppm (C-2,3). Similarly, only the C-2,5 signals of D-mannitol move up-frequency upon silicate complexation, shifting from 71.4 ppm to 74.2 and 74.5 ppm.
26. Carbon-13 NMR investigations into the interaction between aqueous borates and polyols reveal similar high-frequency shifts upon complex formation [A. Munoz and L. Lamandé, Carbohydrate Res. 225, 113 (1991)]. Consistent with our observations, the structural criterion for optimal borate complex formation appears to be that the polyols contain a three hydroxy pair. However, the boron center appears to bind across the threo pair itself, rather than at sites adjacent to it. Moreover, boron does not undergo an increase in coordination number.
27. 13C NMR signals occur at 66.0 (C-1,4) and 70.2 ppm (C-2,3).
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33. We thank J. T. Banks for helpful discussions and R. J. Kirkpatrick for the generous loan of isotopically enriched silica. Funding was provided in part by NIH (PHS 1 S10 RR 10444-01; GM-42208 and RR 01811), NSF (NSF CHE 96-10502), and the Natural Sciences and Engineering Council of Canada (NSERC). Facilities were provided by the NIH-supported Illinois EPR Research Center, and the NSERC-supported Prairie Regional NMR Centre (Winnipeg).