The reactions of trichloromethylium with oxygen- and sulfur-containing compounds
The gas phase reactions of CCl3+ with acetone, diethyl ketone, dimethyl ether, diethyl ether, several cyclic ethers, sulfides, and disulfides have been examined using high pressure mass spectrometry. In many of the reactions a stabilized ion–molecule complex is observed which may or may not react further. With disulfides a second reaction channel is electron transfer, the observation of which shows that the 0–0 ionization energies of these compounds are lower than the ionization energy of CCl3 (8.28 eV) and hence lower than the values obtained by photoelectron spectroscopy. Rate constants for the disappearance of CCl3+ in general show an increase in value with increase in reaction exothermicity. The lack of a measurable effect of pressure on rate constants is discussed for some association reactions which have reaction efficiencies well below unity.