The gas-phase reactivities of several protonated quinoline-based sigma-type (carbon-centered) mono-, bi-, and triradicals toward dimethyl disulfide (DMDS) were studied by using a linear quadrupole ion trap mass spectrometer. The mono- and biradicals produce abundant thiomethyl abstraction products and small amounts of DMDS radical cation, as expected. Surprisingly, all triradicals produce very abundant DMDS radical cations. A single-step mechanism involving electron transfer from DMDS to the triradicals is highly unlikely because the (experimental) adiabatic ionization energy of DMDS is almost 3 eV greater than the (calculated) adiabatic electron affinities of the triradicals. The unexpected reactivity can be explained based on an unprecedented two-step mechanism wherein the protonated triradical first transfers a proton to DMDS, which is then followed by hydrogen atom abstraction from the protonated sulfur atom in DMDS by the radical site in the benezene ring of the deprotonated triradical to generate the conventional DMDS radical cation and a neutral biradical. Quantum chemical calculations as well as examination of deuterated and methylated triradicals provide support for this mechanism. The proton affinities of the neutral triradicals (and DMDS) influence the first step of the reaction while the vertical electron affinities and spin-spin coupling of the neutral triradicals influence the second step. The calculated total reaction exothermicities for the triradicals studied range from 27.6 up to 29.9 kcal mol(-1).