Kinetics of the Allylic Amination of Olefins by Nitroarenes Catalyzed by [CpFe(CO)₂]₂

The kinetics of the [CpFe(CO)₂]₂-catalyzed allylic amination of α-methylstyrene derivatives by nitroarenes is reported. The reaction is found to be first-order in both alkene and nitroarene, zero-order in CO, and half-order in catalyst. Relative rate studies of para-substituted alkenes and nitroarenes show that the rate is increased for electron-deficient nitro compounds and for electron-rich alkenes. On the basis of these results, together with the regioselectivity of the reactions with unsymmetrical alkenes and the outcome of trapping experiments for free nitrosoarenes and nitrenes, a mechanistic scheme is proposed involving C−N bond formation from a CpFe(CO)(RNO)(alkene) intermediate.