Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Abstract

The mechanism of the reaction of ground state oxygen atoms, O(3P), with CH3SSCH3 was studied by analysis of the final products. Oxygen atoms were generated by mercury photosensitized decomposition of N2O such that [Formula: see text]. The only detected product was CH3S(O)2SCH3, which accounted for close to 70% of the oxygen atoms reacted. Isomerization of small amounts of cis- or trans-2-butene added to the reaction mixture indicated the presence of CH3S radicals. The results are consistent with the primary reaction O + CH3SSCH3 → CH3SO + CH3S. The effect of small amounts of CH3SH and H2S on the yields of CH3S(O)2SCH3 and the products formed provide further information on the nature of the secondary chemistry. A comprehensive reaction mechanism has been proposed.

Kinetics of the reactions of hydroxyl radicals with aldehydes studied under atmospheric conditions

“…For the 0(3P) atom reactions the Arrhenius parameters were measured (22), and, since the A factors were approximately constant throughout the C2-C4 aldehydes studied, the increasing rate constants corresponded to slightly decreasing activation energies in going from C2 to C4 aldehydes. This trend was taken to indicate a slight weakening of the aldehydic C-H bond in going from C2 to C4 (22). For the hydroxyl radicals the temperature coefficients have been measured for formaldehyde (14,16) and acetaldehyde (14), and the activation energies found to be close to zero.…”

Matrix isolation and spectroscopic properties of the methylsulfinyl radical CH3(O)S˙

“…8 Methods for the generation of 3 comprise photochemical 9 or multiphoton IR absorption, 10 decomposition of DMSO, or the reaction of 1 with atomic oxygen. 7,11 The focus of atmospheric chemistry studies was the determination of reaction rates for scavenging of 3 with O 2 , O 3 , and NO 2 . 12 However, many uncertainties concerning the reaction pathways and involved intermediates still exist.…”

Exploring the synthetic application of sulfinyl radicals

“…This pathway was first proposed by Topping et al in 1962. 11 Despite the lack of direct experimental evidence, this pathway gained support from a number of chemists over the next two decades, including Oae, 12,41 Kice, 13,14,42 Miller, 15 Koch, 16 Howard, 40 Iino, 43 Freeman, [44][45][46][47] Singleton, 48 Bennett 49 and so on. Harpp et al designed a class of cyclic thiosulfinates (1a and 1b) and used nuclear magnetic resonance (NMR) to detect their oxidation in real time, which provides the first direct experimental evidence for the sulfinyl radical self-termination via the S-O coupling pathway (Table 3).…”

“…This pathway was first proposed by Topping et al in 1962. 11 Despite the lack of direct experimental evidence, this pathway gained support from a number of chemists over the next two decades, including Oae, 12,41 Kice, 13,14,42 Miller, 15 Koch, 16 Howard, 40 Iino, 43 Freeman, 44–47 Singleton, 48 Bennett 49 and so on.…”