A Mechanistic Study on the Reaction of Non‐Heme Diiron(III)‐Peroxido Complexes with Benzoyl Chloride

Dinuclear iron peroxido complexes are important intermediates for selective oxidation reactions. A detailed kinetic study of the reaction benzoyl chloride (BzCl) with a dinuclear non-heme cis end-on complex ligand EtHPTB (N,N,N′,N′-tetrakis[(N-ethyl-2-benzimidazolyl)methyl]-2-hydroxy-1,3-diamino-propane) had been performed. The starting complex, can be obtained either by iron(II) O2 or instead, applying corresponding iron(III) together hydrogen peroxide. Using low temperature stopped-flow measurements allowed to obtain activation parameters and in combination Hammet plot it was possible postulate mechanism formation perbenzoate prior its decomposition. Furthermore, direct peracetic acid analyzed. Additionally, comparison mononuclear bztpen (N-benzyl-N,N′,N′-tris(2-pyridylmethyl)ethane-1,2-diamine) investigated as well.