Work

Basicity of Nucleophilic Carbenes in Aqueous and Nonaqueous SolventsTheoretical Predictions

Year: 2004

Type: 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 pKa 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 pKa'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.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja038973x

Authors: Alison M. Magill, Kingsley J. Cavell, Brian F. Yates

Institutions: University of Tasmania, Cardiff University

Language: English

Topic: Physical Organic Chemistry and Reaction Kinetics

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

OpenAlex ID: W2006567571

FWCI: 16.6

Cites: 46

Cited by: 461

Related to: 10