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A Theoretical Study of Fluorine Atom and Fluoride Ion Attack on Methane and Silane
Journal of the American Chemical Society (1985)
  • Larry P. Davis, United States Air Force Academy
  • Larry W. Burggraf, United States Air Force Academy
  • Mark S. Gordon
  • Kim K. Baldridge
Abstract

We have performed MNDO and ab initio calculations for reactions of fluorine atom attack on methane and silane and, in addition, fluoride ion attack on the same molecules in the case of MNDO. We modeled both substitution and abstraction reactions in each case. Results were compared with experimental data, where available. Comparisons show that MNDO usually does as well as the ab initio methods in reproducing experimental values for D.E's of these reactions, but MNDO predicts activation barriers too high in most cases. Nevertheless, MNDO does qualitatively agree with the ab initio result that, while carbon undergoes abstraction much more easily than substitution, silicon can undergo either substitution or abstraction quite easily. The analysis in the case of fluoride ion attack on silane is complicated by the predicted ease of formation of a stable trigonal-bi pyramidal intermediate.

Disciplines
Publication Date
July, 1985
Publisher Statement
Reprinted (adapted) with permission from Journal of the American Chemical Society 107 (1985): 4415, doi:10.1021/ja00301a008. Copyright 1985 American Chemical Society.
Citation Information
Larry P. Davis, Larry W. Burggraf, Mark S. Gordon and Kim K. Baldridge. "A Theoretical Study of Fluorine Atom and Fluoride Ion Attack on Methane and Silane" Journal of the American Chemical Society Vol. 107 Iss. 15 (1985)
Available at: http://works.bepress.com/mark_gordon/48/