A Theoretical Study of Fluorine Atom and Fluoride Ion Attack on Methane and Silane

Article abstract of DOI:10.1021/ja00301a008

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 ΔE'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-bipyramidal intermediate.