Facile Formation of Stable Neutral Radicals and Cations from [22]Smaragdyrin BF₂ Complexes

Abstract

meso-Trimesityl-substituted [20]smaragdyrin freebase was synthesized by p-toluenesulfonic acid catalyzed reaction of 5-mesityldipyrromethane and 2,14-dibromodipyrrin in an improved yield of 63 %. Unexpectedly, treatment of the [20]smaragdyrin freebase with BF₃ ⋅ OEt₂ and triethylamine (TEA) gave a stable radical species, in which the BF₂ unit is coordinated at the tripyrrin site, probably by ready release of a hydrogen atom of a [22]smaragdyrin BF₂ complex. Similar treatment of [22]smaragdyrin free base produced another [22]smaragdyrin BF₂ complex, in which the BF₂ unit is coordinated at the dipyrrin site. The tripyrrin site coordinated neutral radical was oxidized with AgSbF₆ to give a stable antiaromatic cation; this was reduced with NaBH₄ to its 22π congener, which was easily oxidized back to the neutral radical in the air and rearranged to thermodynamically stable dipyrrin site coordinated [22]smaragdyrin BF₂ complex upon treatment with BF₃ ⋅ OEt₂ and TEA. Further, the dipyrrin site coordinated [22]smaragdyrin BF₂ complex was similarly oxidized to a stable neutral radical and a stable cation in a stepwise manner. This work demonstrates a rare ability of smaragdyrin BF₂ complexes to exist in multiple redox states, particularly forming a stable neutral radical by facile release of a hydrogen atom.