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 [FeIII 2 (μ-O2 )(MeBzim-Py)4 (CH3 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 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.