Fe or Fe-NO catalysis? A quantum chemical investigation of the [Fe(CO) 3(NO)]--catalyzed cloke-wilson rearrangement

Abstract

A quantum chemical investigation of the Bu4N[Fe(CO) 3(NO)]-catalyzed Cloke-Wilson rearrangement of vinyl cyclopropanes is reported. It was found that allylic C-C bond activation can proceed through a SN2 or SN2-type mechanism. The application of the recently reported intrinsic bond orbital (IBO) method for all structures indicated that one Fe-N π bond is directly involved. Further analysis showed that during the reaction oxidation occurs at the NO ligand exclusively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.