The reactivity of the previously reported peroxo adduct[ Fe III 2 (m-O 2 )(MeBzim-Py) 4 (CH 3 CN) 2 ] 4 + (1)( MeBzim-Py = 2-(2'-pyridyl)-N-methylbenzimidazole) towards aldehyde substrates including phenylacetaldehyde( PAA), hydrocinnamaldehyde (HCA), propionaldehyde (PA), 2-phenylpropionaldehyde (PPA), cyclohexanecarboxaldehyde (CCA), and para-substituted benzaldehydes (benzoyl chlorides) has been investigated. Complex 1 provedtobeanucleophilic oxidant in aldehyde deformylation reaction. These models, including detailed kinetic and mechanistic studies, may serve as the first biomimicso fa ldehyde deformylating oxygenase (ADO) enzymes. Scheme1.[Fe III2 (m-O 2 )(MeBzim-Py) 4 (CH 3 CN) 2 ] 4 + (1).

The complex [FeIII2(-O2)(L3)4(CH3CNS)2]4+ (L3 = 2-(4-thiazolyl)benzimidazole, S = solvent) forms upon reaction of [FeII(L3)2] with H2O2 and is a functional model of peroxo-diiron intermediates invoked during the catalytic cycle of...

The ambiphilic behavior (electrophilic versus nucleophilic character) of the peroxo-diferric complex and its relative reactivity towards aldehydes and phenols have been discussed.