American Chemical Society
jp7b02415_si_001.pdf (384.25 kB)

Temperature and Pressure Dependences of the Reactions of Fe+ with Methyl Halides CH3X (X = Cl, Br, I): Experiments and Kinetic Modeling Results

Download (384.25 kB)
journal contribution
posted on 2017-05-10, 00:00 authored by Shaun G. Ard, Nicholas S. Shuman, Oscar Martinez, Nicholas R. Keyes, Albert A. Viggiano, Hua Guo, Jürgen Troe
The pressure and temperature dependences of the reactions of Fe+ with methyl halides CH3X (X = Cl, Br, I) in He were measured in a selected ion flow tube over the ranges 0.4 to 1.2 Torr and 300–600 K. FeX+ was observed for all three halides and FeCH3+ was observed for the CH3I reaction. FeCH3X+ adducts (for all X) were detected in all reactions. The results were interpreted assuming two-state reactivity with spin-inversions between sextet and quartet potentials. Kinetic modeling allowed for a quantitative representation of the experiments and for extrapolation to conditions outside the experimentally accessible range. The modeling required quantum-chemical calculations of molecular parameters and detailed accounting of angular momentum effects. The results show that the FeX+ products come via an insertion mechanism, while the FeCH3+ can be produced from either insertion or SN2 mechanisms, but the latter we conclude is unlikely at thermal energies. A statistical modeling cannot reproduce the competition between the bimolecular pathways in the CH3I reaction, indicating that some more direct process must be important.