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Basicity of Nucleophilic Carbenes in Aqueous and Nonaqueous Solvents - Theoretical Predictions
Citation
Magill, AM and Cavell, KJ and Yates, BF, Basicity of Nucleophilic Carbenes in Aqueous and Nonaqueous Solvents - Theoretical Predictions, Journal of the American Chemical Society, 126, (28) pp. 8717-8724. ISSN 0002-7863 (2004) [Refereed Article]
Abstract
The complete basis set method CBS-QB3 was used in conjunction with the CPCM solvation model to predict both the absolute and relative pKa's of 12 nucleophilic carbenes in dimethyl sulfoxide (DMSO), acetonitrile (MeCN), and water. Average absolute pKa values in DMSO ranged from 14.4 ± 0.16 for 3-methylthiazol-2-ylidene (12) to 27.9 ± 0.23 in the case of bis(dimethylamino)carbene (11), while values in MeCN were determined to be between 25.7 ± 0.16 (12) and 39.1 ± 0.25 (11). Relative pK a calculations yielded similar results. Calculations in aqueous solution gave pKa's between 21.2 ± 0.2 (12) and 34.0 ± 0.3 (11). Excellent agreement between calculated and experimental pK a's was obtained for the few cases where experimental numbers are available, confirming that this theoretical approach may be used to calculate highly accurate pKa values.
Item Details
| Item Type: | Refereed Article |
|---|---|
| Research Division: | Chemical Sciences |
| Research Group: | Organic Chemistry |
| Research Field: | Physical Organic Chemistry |
| Objective Division: | Expanding Knowledge |
| Objective Group: | Expanding Knowledge |
| Objective Field: | Expanding Knowledge in the Chemical Sciences |
| Author: | Magill, AM (Miss Alison Magill) |
| Author: | Cavell, KJ (Professor Kingsley Cavell) |
| Author: | Yates, BF (Professor Brian Yates) |
| ID Code: | 31988 |
| Year Published: | 2004 |
| Web of Science® Times Cited: | 337 |
| Deposited By: | Chemistry |
| Deposited On: | 2004-08-01 |
| Last Modified: | 2005-05-30 |
| Downloads: | 0 |
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