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Anomeric effect plays a major role in the conformational isomerism of fluorinated pnictogen compounds
Author(s) -
Martins Levindo E.,
Freitas Matheus P.
Publication year - 2008
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.1397
Subject(s) - chemistry , anomeric effect , isodesmic reaction , pnictogen , conformational isomerism , vicinal , hyperconjugation , antibonding molecular orbital , lone pair , stereochemistry , crystallography , anomer , computational chemistry , density functional theory , molecule , organic chemistry , atomic orbital , physics , superconductivity , quantum mechanics , electron
According to our theoretical studies, the anomeric effect, an stereoelectronic interaction between lone pair and a vicinal antibonding orbital, has shown to contribute decisively for the conformational isomerism of 1‐fluoro‐ N,N ‐dimethylmethanamine ( 1 ) and of its corresponding P, As and Sb analogues ( 2 – 4 ). CX bonds in 2 – 4 are larger than in the parent compound 1 , thus providing a LP X /CF * interaction progressively weaker on going from 1 to 4 . However, such hyperconjugation contributed by more than 1.3 kcal mol −1 for the stabilization of anti conformer in 4 ( θ LPXCF = 180°), increasing to 24.1 kcal mol −1 in 1 . An isodesmic reaction model supported these findings. Copyright © 2008 John Wiley & Sons, Ltd.