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Calculational Study of Fluoroammonium and Related Cations and Dications
Author(s) -
Olah George A.,
Prakash G. K. Surya,
Rasul Golam
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900335
Subject(s) - chemical shift , chemistry , fluorine , ion , inductive effect , fluorine 19 nmr , computational chemistry , ab initio , carbon 13 nmr , nitrogen , crystallography , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry
Abstract Structures as well as 15 N and 19 F NMR chemical shifts of a series of fluoroammonium ions were studied by ab initio/GIAO‐SCF, GIAO‐MP2 and GIAO‐CCSD(T) methods. Calculated 15 N and 19 F NMR chemical shifts correlate well with the experimental data. The relative stabilities as well as the charge of the central nitrogen atom of fluoro‐substituted tetrahedral ammonium ions were found to increase linearly with the increasing number of fluorine substituents due to their strong electron‐withdrawing inductive effect. Similarly the magnitude of 15 N NMR chemical shifts also increase linearly with the increasing number of fluorine substituents in accord with the strong deshielding effect of fluorine. Structures as well as 15 N and 19 F NMR chemical shifts of yet experimentally unknown fluoroammonium dications were also computed.