Photochemical Generation and Reactivity of Naphthyl Cations: cine Substitution

The photochemical solvolyses of naphthalen-1-yl(phenyl)iodonium tetrafluoroborate and naphthalen-2-yl(phenyl)iodonium tetrafluoroborate in methanol regiospecifically yield the naphthalen-1- and -2-yl ethers but afford scrambled 1- and 2-phenylnaphthalene Friedel-Crafts products. It is demonstrated that singlet naphthyl cations account for the formation of the naphthyl ethers, but that the cine substitution is most likely to be due to the intermediacy of triplet naphthyl cations. According to the experiments reported here, the singlet naphthyl cations are lower in energy than their triplet isomers. High-level MO calculations for the cations in methanol support this finding.