Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide

Artur Mardyukov and Peter R. Schreiner
Acc. Chem. Res. 2018, 51, 475–483. DOI: 10.1021/acs.accounts.7b00536

The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation. The reaction of ·OH with DMS is known to proceed by two independent channels: abstraction and addition. The oxidation of DMS is believed to be initiated by the reaction with ·OH and NO₃· radicals, which eventually leads to the formation of sulfuric acid (H₂SO₄) and methanesulfonic acid (CH₃SO₃H). The reaction of DMS with NO₃· appears to proceed exclusively by hydrogen abstraction. The oxidation of DMS consists of a complex sequence of reactions. Depending on the time of the day or altitude, it may take a variety of pathways. In general, however, the oxidation proceeds via chains of radical reactions. Dimethyl sulfoxide (DMSO) has been reported to be a major product of the addition channel. Dimethyl sulfone (DMSO₂), SO₂, CH₃SO₃H, and methanesulfinic acid (CH₃S(O)OH) have been observed as products of further oxidation of DMSO. Understanding the details of DMS oxidation requires in-depth knowledge of the elementary steps of this seemingly simple transformation, which in turn requires a combination of experimental and theoretical methods. The methylthiyl (CH₃S·), methylsulfinyl (CH₃SO·), methylsulfonyl (CH₃SO₂·), and methylsulfonyloxyl (CH₃SO₃·) radicals have been postulated as intermediates in the oxidation of DMS. Therefore, studying the chemistry of sulfur-containing free radicals in the laboratory also is the basis for understanding the mechanism of DMS oxidation in the atmosphere. The application of matrix-isolation techniques in combination with quantum-mechanical calculations on the generation and structural elucidation of CH₃SO_x (x = 0–3) radicals is reviewed in the present Account. Experimental matrix IR and UV/vis data for all known species of this substance class are summarized together with data obtained using other spectroscopic techniques, including time-resolved spectroscopy, electron paramagnetic resonance spectroscopy, and others. We also discuss the reactivity and experimental characterization of these species to illustrate their practical relevance and highlight spectroscopic techniques available for the elucidation of their geometric and electronic structures. The present Account summarizes recent results regarding the preparation, characterization, and reactivity of various radical species with the formula CH₃SO_x (x = 0–3).