Manganese-alkylperoxo species (Mn-OOR) are proposed to be important intermediates in a number of biological systems, notably manganese lipoxygenase and a manganese-dependent dioxygenase, and could be of importance in small-molecule manganese oxidation catalysts. Unfortunately, characterization of these alkylperoxo manganese intermediates remains elusive. As such, in an effort to understand more about their structural properties and reactivity, model complexes are heavily relied on. Here we describe a [MnIII(dpaq)(OOtBu)]+ complex, which was produced by treating MnII(dpaq)(OTf) with tert-butyl hydroperoxide and triethylamine in acetonitrile at 0°C. The [MnIII(dpaq)(OOtBu)]+ features the pentadentate dpaq ligand, with four equatorial nitrogen atoms and one axial amide donor. Formation of the Mn(III)-alkylperoxo adduct was confirmed via UV-vis spectroscopy and mass spectrometry. Of note is the high stability of this species in solution and at ambient conditions, which we expect will facilitate further structural and spectroscopic characterization. We will also discuss the consequences of a strongly donating trans amide ligand on the activation of the alklyperoxo ligand.

Characterization and reactivity of a Mn(III)-alkylperoxo species supported by an amide-containing ligand

251st National Meeting (2016)

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