Molecular self-modification: homolog of a manganese laundry bleach catalyst oxidatively transforms its tetradentate ligand into a novel hexadentate derivative

On the basis of mass spectral studies alone, the relatively new manganese complex, Mn(Et₂EBC)Cl₂ (Et₂EBC = 4,11-diethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), a homolog of the well proven, peroxide-based laundry bleach, Mn(Me₂EBC)Cl₂, has been reported to undergo a sequence of 2-electron oxidation steps, ultimately converting its ethyl groups into chelated ethoxo and methylene carboxylato groups, [Mn^IV{(^?OCH₂CH₂)(^?O₂CCH₂)}EBC)](PF₆)₂. We report here the isolation and characterization of that unusual product, and provide insight into the remarkable catalytic pathway to its formation. At temperatures above 0 °C, oxidation by aqueous H₂O₂ reliably transforms Mn(Et₂EBC)Cl₂ into [Mn^IV{(^?OCH₂CH₂)(^?O₂CCH₂)}EBC)]²⁺. The experimental data for this intramolecular ethyl group transformation is consistent with oxygen insertion into a methyl C?CH moiety of the ethyl group, ?CNCH₂C(?CH)H₂, by the Mn^IV?COOH functional group.