Factors controlling the barriers to degenerate hydrogen atom transfers

J Am Chem Soc. 2005 Apr 27;127(16):5794-5. doi: 10.1021/ja050024b.

Abstract

High-level electronic structure calculations have been used to study the factors contributing to the barriers to degenerate hydrogen-atom transfer (HAT) reactions. Understanding of these reactions is a prerequisite to the development of any more general theory of HAT reactions, and yet, the existing models for such reactions perform quite poorly when applied to even simple self-exchanges. The reasons behind these failures are elucidated in the present work. They include a near cancellation of bond-strength effects between reactant and transition state, as well as a strong dependence of the geometry of the transition state on the nature of the heavy atoms.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Ammonia / chemistry
  • Hydrofluoric Acid / chemistry
  • Hydrogen / chemistry*
  • Hydrogen Peroxide / chemistry
  • Hydroxylamine / chemistry
  • Kinetics
  • Methane / chemistry
  • Models, Molecular
  • Thermodynamics
  • Water / chemistry

Substances

  • Water
  • Hydroxylamine
  • Ammonia
  • Hydrogen
  • Hydrogen Peroxide
  • Methane
  • Hydrofluoric Acid