Quantum mechanical analysis of decomposition pathways of chloromethyl hypochlorite

The most important decomposition pathways of chloromethyl hypochlorite, ClCH2OCl, are examined using molecular structure quantum mechanical techniques. Specifically, the 1,1 and 1,2 elimination reactions, the isomerization channel and the C-O, O-Cl bond scissions are considered. The theoretical investigation yields high barriers for all production channels, which emphasize the high stability of ClCH2OCl. Among the various reaction pathways, only the 1,2 eliminations to CH2O+Cl2 and ClCHO+HCl and the isomerization to dichloromethanol lead to more stable species. The photolytic O-Cl bond scission presents the lowest critical energy for reaction at the CCSD(T) level. Comparison with literature reports about the decomposition scheme of simple methyl hypochlorite, CH3OCl, and fluoromethyl hypochlorite, FCH2OCl, indicates a moderate effect of the different substitute on the dissociation pattern of these compounds.