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 CCl
4 as a transient product suggests a mechanism that can lead to trichloromethyl radicals. A mechanism postulating formation of the hypervalent intermediate Cl
3C
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 XeF
2 at the glass surface competes and limits the lifetime of the reagent under these conditions.