Cation Radicals. 48. Evidence for Electron Transfer in the Alkylation of Thianthrene Cation Radical with Diethylmercury

Article abstract of DOI:10.1021/jo00150a001

Evidence is presented that reaction of thianthrene cation radical (Th(1+)<*>) with Et2Hg in acetonitrile occurs by way of initial electron transfer.Products of reaction are thianthrene (Th), 5-ethylthianthrenium perchlorate (ThEt(1+)*ClO4(1-)), and EtHg(1+).When reaction is carried out under 18O2, not only the same products are formed but also thianthrene oxide (ThO), thianthrene dioxide (ThO2), acetaldehyde, and ethanol, all of which are enriched with 18O.Reaction therefore appears to lead initially to Et2Hg(1+)<*> from which ethyl radicals are formed and are trapped with Th(1+)<*> and O2.Reactions of EtO2<*> are believed to lead to the products containing 18O.Reaction of Ph2Hg with Th(1+)<*> does not appear to follow this pathway.