Stoichiometric Aldehyde Deformylation Mediated by Nucleophilic Peroxo-diiron(III) Complex as a Functional Model of Aldehyde Deformylating Oxygenase

The reactivity of the previously reported peroxo adduct [Fe-2(III)(mu-O-2)(MeBzim-Py)(4)(CH3CN)(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 proved to be a nucleophilic oxidant in aldehyde deformylation reaction. These models, including detailed kinetic and mechanistic studies, may serve as the first biomimics of aldehyde deformylating oxygenase (ADO) enzymes.