Thiol radical cations and thiyl radicals as direct products of the free electron transfer from aromatic thiols to n-butyl chloride radical cations

Radical and ionic reactions were observed in the pulse radiolysis of thiophenols (ArSH=thiophenol, o-, m- and p-thiocresol or 2-thionaphthol) in n-butyl chloride solution. The main source of aromatic thiyl radicals is the reaction of butyl radicals with the thiols, which proceeds at 1.0–5.6×108 dm3 mol−1 s−1. This radical generation path is completely quenched in the presence of oxygen. Under these conditions, only the electron transfer reaction between n-butyl chloride parent ions and the thiophenols remains and could be well analyzed. It takes place at a rate constant of about 1.5×1010 dm3 mol−1 s−1 and takes two parallel paths–common electron transfer yielding thiophenol radical cations and a more complex ionic reaction resulting directly in thiyl radicals. The latter is thought to proceed via an encounter complex geometry, ArSH···ClBu•+, in which electron transfer is directly followed by immediate deprotonation. The thiyl radicals and the thiol radical cations are characterized by their optical absorption spectra and their kinetic properties. Quantum chemical calculations underpin our mechanistic interpretation and provide information about the charge distribution and reactivity of the thiol radical cations.