Dimethoxymethane-Hydrogen Chloride Interaction: Gas Phase versus Low-Temperature Behavior Studied Using Matrix Isolation Infrared and Density Functional Theory Methods

作者：Sundararajan K^*; Ramanathan N

来源：Journal of Physical Chemistry A, 2013, 117(11): 2347-2357.

DOI：10.1021/jp400332v

Premixing of dimethoxy methane (DMM) and hydrogen chloride (HCl) with Ar/N-2 in the gas phase resulted in a nucleophilic substitution reaction and yielded products, cis-chloromethyl methyl ether (cis-CMME) and methanol. On the contrary, when DMM and HCl were separately codeposited in a low-temperature Ar matrix produced hydrogen-bonded alkoxy adduct, probably the intermediate in the gas phase nucleophilic substitution reaction. The formation of the alkoxy adduct was evidenced by the shifts in the vibrational frequencies of the DMM and HCl submolecules. The structure and energy of the alkoxy adduct were computed at the B3LYP/6-311++G** level of theory. The computations indicated only one minimum for the DMM-HCl adduct. The nucleophilic substitution reaction between DMM and HCl is prevented in the low-temperature matrix probably due to the cage effect in the matrix.

• 出版日期2013-3-21