The reaction of xenon difluoride with chloroform

The reaction of xenon difluoride with chloroform in PTFE–FEP, Pyrex and quartz tubes has been studied using 19F and 13C NMR spectroscopy. The detection of CCl4 as a transient product suggests a mechanism that can lead to trichloromethyl radicals. A mechanism postulating formation of the hypervalent intermediate Cl3CXeF is proposed. In PTFE–FEP, the initiation of reaction is slow but in Pyrex reaction begins immediately due to Lewis acid sites on the glass surface. In Pyrex and quartz, an alternative decomposition of XeF2 at the glass surface competes and limits the lifetime of the reagent under these conditions.