Thermal reactions of thiyl radicals

Synthesis, Structure, and Physicochemical Characteristics of Thiols

“…For instance arenethiyl radicals possess higher value of the formation enthalpy as compared to that of alkanethiyl radicals; the formation enthalpy for the benzenethiyl radical equals to 237.6 ± 9 kJ mol -1 [19]. The enthalpy of formation in the series of alkanethiyl radicals diminishes with the growing length and branching of the alkyl chain from 129.7 kJ mol -1 for methanethiyl to 61.8 kJ mol -1 for butanethiyl and 46 kJ mol -1 for 2-methyl-1-propanethiyl radicals [19]. The electron affinity of thiyl radicals is higher than that of oxyl radicals due to the presence of vacant d-orbitals in the sulfur atom.…”

“…The character and structure of groups attached to sulfur in the thiol affect significantly the enthalpy of formation of thiyl radicals [19,35]. For instance arenethiyl radicals possess higher value of the formation enthalpy as compared to that of alkanethiyl radicals; the formation enthalpy for the benzenethiyl radical equals to 237.6 ± 9 kJ mol -1 [19].…”

“…The homolysis of the SH bond in thiols yields thiyl radicals that play extremely important part in various chemical reactions [19,31], in particular, in the polymerization proceses [32]. The homolysis of the SH bond in thiols can be performed by photochemical [19,33], radiation [19], thermal [19,31], and chemical [19,34] effect.…”

“…The homolysis of the SH bond in thiols can be performed by photochemical [19,33], radiation [19], thermal [19,31], and chemical [19,34] effect. The chemical procedure is the most widely applied.…”

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

“…Thiol‐ene reactions can proceed by either a radical mechanism or in a base catalyzed fashion (Michael addition) . The well‐known radical‐mediated thiol‐ene reaction can be initiated by UV‐light in the presence of a photoinitiator or by heat in the presence of a thermal initiator . Recently, new pathways for initiating/catalyzing the thiol‐ene reaction have been explored.…”