Factors controlling the barriers to degenerate hydrogen atom transfers.
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.
Isborn
Christine
C
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA.
Hrovat
David A
DA
Borden
Weston Thatcher
WT
Mayer
James M
JM
Carpenter
Barry K
BK
D000641:Ammonia / Q000737:chemistry; D006858:Hydrofluoric Acid / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D019811:Hydroxylamine / Q000737:chemistry; D007700:Kinetics; D008697:Methane / Q000737:chemistry; D008958:Models, Molecular; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D014867:Water; D019811:Hydroxylamine; D000641:Ammonia; D006859:Hydrogen; D006861:Hydrogen Peroxide; D008697:Methane; D006858:Hydrofluoric Acid