(Anthracen-9-yl)methyl sulfides as a mechanistic probe for chemical as well as photochemical electron-transfer reactions

Abstract

We have examined the intermediacy of sulfur-centred radical cations in the one-electron oxidation of (anthracen-9-yl)methyl sulfides. Reaction of (anthracen-9-yl)methyl sulfides with ceric ammonium nitrate (CAN) gave predominantly nitration and oxidation products along with products arising through sulfur-centred radical cations in minor amounts. Upon irradiation, (anthracen-9-yl)methyl sulfides underwent efficient intramolecular single electron transfer leading to a variety of products arising through the intermediacy of sulfur-centred radical cations.

Crystal structures of 9-[bis(benzylsulfanyl)methyl]anthracene and of cyclo-dodecakis(μ2-phenylmethanethiolato-κ2 S:S)hexapalladium(6 Pd—Pd)–anthracene-9,10-dione (1/1)

“…We have not examined the mechanistic aspects of this unexpected reaction in detail, but the fact that Pd6 co-crystallizes with one molecule of anthracene-9,10-dione and smaller amounts of 9-anthraldehyde is in line with this hypothesis. It is noteworthy that this diketone has also been detected as one of the numerous Synthesis scheme for L1 and the cluster Pd6ÁC 14 H 8 O 2 oxidation products stemming from the oxidation of (anthracen-9-ylmethyl)(benzyl)sulfane with ceric ammonium nitrate (Gopalakrishnan et al, 2015).…”