The [(Bn-tpen)Fe] Complex as a Catalyst for the Oxidation of Cyclohexene and Limonene with Dioxygen.

(Bn-tpen)Fe(MeCN), containing the pentadentate Bn-tpen--benzyl-,,-tris(2-pyridylmethyl)-1,2-diaminoethane ligand, was studied in the oxygenation of cyclohexene and limonene using low-pressure dioxygen (0.2 atm air or 1 atm pure O) in acetonitrile. 2-Cyclohexen-1-one and 2-cyclohexen-1-ol are the main products of cyclohexene oxidations, with cyclohexene oxide as a minor product. Limonene is oxidized to limonene oxide, carvone, and carveol. Other oxidation products such as perillaldehyde and perillyl alcohol are found in trace amounts. This catalyst is slightly less active than the previously reported (N4Py)Fe(MeCN) (N4Py--bis(2-pyridylmethyl)--(bis-2-pyridylmethyl)amine). Based on cyclic voltammetry experiments, it is postulated that [(Bn-tpen)Fe=O] is the active species. The induction period of approx. 3 h during cyclohexene oxygenation is probably caused by deactivation of the reactive Fe(IV)=O species by the parent Fe(II) complex. Equimolar mixtures of Fe(II) salt and the ligand (in situ-formed catalyst) gave catalytic performance similar to that of the synthesized catalyst.