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Ab initio quantum‐mechanical calculations on trifluoromethylamine
Author(s) -
Heaton M. M.,
Mills D.
Publication year - 1985
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560280202
Subject(s) - hyperconjugation , chemistry , ab initio , fluorine , ab initio quantum chemistry methods , computational chemistry , decomposition , amine gas treating , molecular geometry , quantum chemistry , inductive effect , electronic structure , bond length , natural bond orbital , crystallography , density functional theory , molecule , organic chemistry , crystal structure , supramolecular chemistry
Extensive ab initio molecular‐orbital calculations were carried out on trifluoromethylamine (TFM) to elucidate changes in geometry and electronic structure upon fluorination. The calculations show that the decomposition of CF 3 NH 2 is slightly endoenergetic, and the heats of atomization of CF 3 NH 2 and CH 3 NH 2 show decreased stability of the species upon fluorination. Characteristic of CF 3 NH 2 is a highly polar, strong, short CN bond. More limited calculations were carried out on CF 3 OH and CH 3 OH, and the electronic structure of CF 3 OH is found to be generally similar to that of CF 3 NH 2 . The reduced basicity of the fluorinated amine cannot be ascribed to the inductive effect; the enhanced acidity of the fluorinated alcohol reflects the weakening of the OH bond. No evidence leads to a confirmation of the existence of nitrogen–fluorine hyperconjugation in the fluorinated amine.