Theoretical Investigation of Superelectrophilic Fluorooxonium Dications FOH32+ and F2OH22+: Comparison with Parent H4O2+ Dication
Structures of the superelectrophilic fluorooxonium dications FOH 3 2+ and F 2OH 2 2+ were calculated at the QCISD(T)/6-311G** level. Proton affinities of their precursor monocationic species were estimated by using G2 theory. For comparison, the parent oxonium dication H 4O 2+ was also calculated at the same level. The O,O- and O,F-diprotonated HFO structures 2c and 2d, respectively, were found to be energy minima. However, the oxonium dication 2c is less stable than the oxonium-fluoronium dication 2d by 14.9 kcal/mol. On the other hand, O,O-diprotonated F 2O 3c was found to be the only minimum for the analogous system. All of these superelectrophilic, dicationic species have substantial kinetic barriers for deprotonations. The possible existence of these dicationic species in either superacidic media or the gas phase is implicated from these studies. The 17O and 19F NMR chemical shifts of the mono- and dictions were also computed by the GIAO-MP2 method.
P. Reddy et al., "Theoretical Investigation of Superelectrophilic Fluorooxonium Dications FOH32+ and F2OH22+: Comparison with Parent H4O2+ Dication," Journal of Physical Chemistry A, vol. 108, no. 18, pp. 4036-4039, American Chemical Society (ACS), May 2004.
The definitive version is available at https://doi.org/10.1021/jp031212w
National Science Foundation (U.S.)
Petroleum Research Fund
Keywords and Phrases
Electronegativity; Oxonium dication; Proton affinity; Superacidic condition; Superelectrophilicity; Chemical bonds; Cyclotron resonance; Fluorine; Fluorine compounds; Nuclear magnetic resonance spectroscopy; Optimization; Polarization; Protons; Reaction kinetics; Positive ions
International Standard Serial Number (ISSN)
Article - Journal
© 2004 American Chemical Society (ACS), All rights reserved.