Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation.

Abstract: Silicon complexation of a [38]octaphyrin (<bold>1</bold>) was accomplished by reaction with an excess amount of MeSiCl3 in the presence of <italic>N</italic>,<italic>N</italic>‐diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex <bold>2</bold>. This complex was interconvertible with an antiaromatic [36]octaphyrin congener (<bold>3</bold>) by oxidation with MnO2 and reduction with NaBH4. Curiously, mild oxidation of <bold>2</bold> with ferrocenium hexafluorophosphate afforded a [37]octaphyrin bis(silicon) complex <bold>4</bold> as an stable radical cation that can be stored under ambient conditions in the solid state. Owing to the two NNNCC‐five‐coordinated Si atoms bearing trigonal bipyramidal geometry, these octaphyrin bis(silicon) complexes take on similar and rigid figure‐of‐eight structures with different consecutive numbers of conjugated π‐electrons (38, 37, and 36), and are all stable. [ABSTRACT FROM AUTHOR]