A study of adducts involving dimethyl sulfide radical cations and methyl halides: Experiment, density functional theory, and unimolecular kinetic modeling. 2c-3e bonding vs hydrogen bonding
Ls. Nichols et Aj. Illies, A study of adducts involving dimethyl sulfide radical cations and methyl halides: Experiment, density functional theory, and unimolecular kinetic modeling. 2c-3e bonding vs hydrogen bonding, J AM CHEM S, 121(39), 1999, pp. 9176-9181
An experimental study of the ion/molecule association reactions in mixtures
of methyl halide and dimethyl sulfide has been performed. MS/MS metastable
and collision-induced dissociation experiments were performed on each [C3H
9SX](.+) association product (X = I, Br, Cl, F) in order to determine struc
tural conformations and to investigate reaction fragmentation pathways. For
X = I, Br, and Cl, a two-center three electron atomic connectivity for the
association adduct giving the following structure [CH3X therefore S(CH3)(2
)](+) was observed. For X = F, the data suggests an F-H-S-bonded associatio
n adduct, [CH2F-H-S(CH3)(2)](.+). Kinetic energy release distributions were
measured for metastable products whenever possible. Furthermore, density f
unctional theory and unimolecular kinetic modeling were carried out to furt
her probe the potential energy surfaces of these radical cations.