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A preliminary quantum‐chemical study of the mechanisms for the reactions of perchlorofluoroethanes with nucleophiles initiated by chlorophilic attacks
Author(s) -
Huang M.B.,
Li X.Y.
Publication year - 1989
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610020203
Subject(s) - chemistry , nucleophile , mndo , hyperconjugation , quantum chemical , gas phase , computational chemistry , medicinal chemistry , photochemistry , organic chemistry , catalysis , molecule
A preliminary theoretical study of the mechanisms for the reactions of the perchlorofluoroethanes CF 2 ClCCl 3 ( 1 ), CF 2 ClCCl 2 F ( 2 ) and CF 3 CCl 3 ( 3 ), with nucleophiles has been carried out by the MNDO method, following the experimentally suggested process shown in Scheme 1. The unlikely chlorophilic attack in the first step of Scheme 1 has been shown to be feasible for 1 , 2 and 3 by analysis of the MO interactions. The second step has been found to be affected by the anionic hyperconjugation which stabilizes the anions CF 2 ClCCl 2 −( 4 ), CF 2 ClCClF − ( 5 ) and CF 3 CCl 2 −( 6 ) and would make reactions (2) (the second step) unfeasible in gas phase, but in solution reaction (2) may still easily occur for 4 and 5 .