Norton, S.H., Bachrach, S.M. and Hayes, Joseph (2005) Theoretical study of nucleophilic substitution at sulfur in sulfinyl derivatives. Journal of Organic Chemistry, 70 (15). pp. 5896-5902. ISSN 00223263
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Official URL: http://dx.doi.org/10.1021/jo050581g
A series of gas-phase nucleophilic substitution reactions at sulfur of methanesulfinyl derivatives by small anions (chloride, cyanide, hydroxide, methoxide, amide, and phosphide, identical to the leaving group in each case) were examined by Hartree-Fock, MP2, and DFT computations. In most cases, substitution was found to follow an addition-elimination mechanism, resulting in a triple-well potential energy surface with small barriers of activation on either side of the central, tetracoordinate-sulfur minimum. The geometries of the central minima, as in the analogous methanesulfenyl cases, are unsymmetrical trigonal bipyramidal, with the nucleophiles and leaving groups occupying apical positions and the sulfur lone pair an equatorial position. The apparent exception, cyanide, may undergo an SN2 displacement.
|Subjects:||Physical sciences > Chemistry|
|Schools:||Faculty of Science and Technology > School of Forensic and Applied Sciences|
|Deposited By:||Joseph Hayes|
|Deposited On:||07 Aug 2013 09:43|
|Last Modified:||15 Mar 2017 10:44|
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