Effects of electrostatic drag on the velocity of hydrogen migration - pre- and post-transition state enthalpy/entropy compensation

Physical Chemistry Chemical Physics : PCCP
Yang-Yang XingDean J Tantillo

Abstract

Ab initio molecular dynamics calculations were used to explore the underlying factors that modulate the velocity of hydrogen migration for 1,2 hydrogen shifts in carbocations in which different groups interact noncovalently with the migrating hydrogen. Our results indicate that stronger electrostatic interactions between the migrating hydrogen and nearby π-systems lead to slower hydrogen migration, an effect tied to entropic contributions from the hydrogen + neighboring group substructures.

References

Oct 1, 1996·Proceedings of the National Academy of Sciences of the United States of America·S MecozziD A Dougherty
Sep 15, 1988·Physical Review A: General Physics·A D Becke
Aug 18, 1999·Proceedings of the National Academy of Sciences of the United States of America·J P Gallivan, D A Dougherty
Aug 5, 1997·Chemical Reviews·Jennifer C. Ma, Dennis A. Dougherty
Mar 20, 2003·Angewandte Chemie·Emmanuel A MeyerFrançois Diederich
May 4, 2006·Journal of the American Chemical Society·Pradeep Gutta, Dean J Tantillo
Jun 8, 2006·Journal of the American Chemical Society·Bryson R UssingDaniel A Singleton
May 22, 2007·The Journal of Nutrition·Dennis A Dougherty
Jan 12, 2008·Accounts of Chemical Research·Yan Zhao, Donald G Truhlar
Sep 15, 2009·Chemical Reviews·Israel FernándezMiguel A Sierra
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
May 24, 2011·Journal of the American Chemical Society·Steven E Wheeler
Dec 12, 2012·Accounts of Chemical Research·Dennis A Dougherty
Jun 8, 2013·Chemistry : a European Journal·Søren Lindbæk BromanMogens Brøndsted Nielsen
Dec 12, 2013·Organic & Biomolecular Chemistry·Michael W LodewykDean J Tantillo
Nov 26, 2014·Journal of the American Chemical Society·Robert M Parrish, C David Sherrill
Apr 9, 2015·Chemical Reviews·Lung Wa ChungKeiji Morokuma
Jun 17, 2020·Angewandte Chemie·Rebecca J BurnsScott Lee Cockroft

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