Document Detail

Theoretical study of nucleophilic substitution at sulfur in sulfinyl derivatives.
MedLine Citation:
PMID:  16018683     Owner:  NLM     Status:  PubMed-not-MEDLINE    
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 S(N)2 displacement.
Steven H Norton; Steven M Bachrach; Joseph M Hayes
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  70     ISSN:  0022-3263     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2005 Jul 
Date Detail:
Created Date:  2005-07-15     Completed Date:  2005-09-12     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  5896-902     Citation Subset:  -    
Department of Chemistry, Trinity University, One Trinity Place, San Antonio, TX 78212, USA.
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