Barriers of hydrogen abstraction vs halogen exchange: an experimental manifestation of charge-shift bonding

Journal of the American Chemical Society
Philippe C HibertySason Shaik

Abstract

This paper shows that the differences between the barriers of the halogen exchange reactions, in the H + XH systems, and the hydrogen abstraction reactions, in the X + HX systems (X = F, Cl, Br), measure the covalent-ionic resonance energies of the corresponding X-H bonds. These processes are investigated using CCSD(T) calculations as well as the breathing-orbital valence bond (BOVB) method. Thus, the VB analysis shows that (i) at the level of covalent structures the barriers are the same for the two series and (ii) the higher barriers for halogen exchange processes originate solely from the less efficient mixing of the ionic structures into the respective covalent structures. The barrier differences, in the HXH vs XHX series, which decrease as X is varied from F to I, can be estimated as one-quarter of the covalent-ionic resonance energy of the H-X bond. The largest difference (22 kcal/mol) is calculated for X = F in accord with the finding that the H-F bond possesses the largest covalent-ionic resonance energy, 87 kcal/mol, which constitutes the major part of the bonding energy. The H-F bond belongs to the class of "charge-shift" bonds (Shaik, S.; Danovich, D.; Silvi, B.; Lauvergnat, D. L.; Hiberty, P. C. Chem. Eur. J. 2005, ...Continue Reading

References

Aug 12, 2000·Chemistry : a European Journal·J M GalbraithP C Hiberty
Oct 14, 2004·Journal of the American Chemical Society·Peifeng SuSason Shaik
Jan 1, 1974·Proceedings of the National Academy of Sciences of the United States of America·S V O'neilC F Bender
Mar 1, 1999·Angewandte Chemie·Sason Shaik, Avital Shurki

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Citations

Oct 11, 2016·The Journal of Physical Chemistry. a·Croix J LaconsayJohn Morrison Galbraith
Nov 23, 2016·Nature Chemistry·Sason ShaikRajeev Ramanan
Jan 5, 2017·Journal of the American Chemical Society·Caiyun GengHelmut Schwarz
Mar 3, 2007·Faraday Discussions·Philippe C HibertySason Shaik
Jun 22, 2017·The Journal of Physical Chemistry. a·Andrew M JamesJohn Morrison Galbraith
Dec 15, 2010·International Journal of Molecular Sciences·Mihai V Putz
Jul 7, 2018·Chemical Society Reviews·Sason ShaikDebasish Mandal
Jun 8, 2012·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Renana Gershoni-Poranne, Amnon Stanger
Oct 25, 2006·Journal of Computational Chemistry·Sason Shaik
Oct 25, 2006·Journal of Computational Chemistry·Philippe C Hiberty, Sason Shaik
Oct 25, 2006·Journal of Computational Chemistry·Peifeng SuSason Shaik
Dec 5, 2006·Journal of Computational Chemistry·T BitterW H E Schwarz
Dec 17, 2008·Angewandte Chemie·Wei WuPhilippe C Hiberty
Oct 14, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sason ShaikPhilippe C Hiberty
Jul 24, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Madhavan Jaccob, Gopalan Rajaraman
Sep 3, 2019·Angewandte Chemie·Sason ShaikPhilippe C Hiberty
Mar 23, 2020·The Journal of Chemical Physics·Mark Dittner, Bernd Hartke
Sep 1, 2009·Nature Chemistry·Sason ShaikPhilippe C Hiberty
Aug 30, 2008·The Journal of Physical Chemistry. a·P Papanikolaou, P Karafiloglou
Mar 12, 2008·The Journal of Physical Chemistry. a·Peifeng SuPhilippe C Hiberty
May 29, 2008·The Journal of Physical Chemistry. a·Andrew DeBlaseJohn Morrison Galbraith
Jun 5, 2013·The Journal of Organic Chemistry·Junming HoJohn Tsanaktsidis
Mar 8, 2018·Journal of the American Chemical Society·Rajeev RamananSason Shaik
Jun 20, 2014·Journal of the American Chemical Society·Cody Ross PittsThomas Lectka
Dec 10, 2013·Journal of Chemical Theory and Computation·José A Gámez, Manuel Yañez
Oct 5, 2013·Journal of the American Chemical Society·Ganna Gryn'ova, Michelle L Coote
May 17, 2019·The Journal of Physical Chemistry Letters·Yao Kun LeiYi Qin Gao
Jun 24, 2020·Journal of the American Chemical Society·Jyothish JoySason Shaik
Nov 23, 2007·The Journal of Physical Chemistry. a·Richard D HarcourtMichelle L Coote
Oct 7, 2021·The Journal of Organic Chemistry·Jyothish JoySason Shaik

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