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

Johannes E M N Klein; Gerald Knizia; Burkhard Miehlich; Johannes Kästner; Bernd Plietker

doi:10.1002/chem.201402716

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

Chemistry. 2014 Jun 10;20(24):7254-7. doi: 10.1002/chem.201402716. Epub 2014 May 9.

Authors

Johannes E M N Klein¹, Gerald Knizia, Burkhard Miehlich, Johannes Kästner, Bernd Plietker

Affiliation

¹ Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany).

PMID: 24817507
DOI: 10.1002/chem.201402716

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.

Keywords: catalysis; cyclopropane; density functional calculations; iron; quantum chemistry.