Two Exceptional Homoleptic Iron(IV) Tetraalkyl Complexes

Alicia Casitas; Julian A Rees; Richard Goddard; Eckhard Bill; Serena DeBeer; Alois Fürstner

doi:10.1002/anie.201612299

Two Exceptional Homoleptic Iron(IV) Tetraalkyl Complexes

Angew Chem Int Ed Engl. 2017 Aug 14;56(34):10108-10113. doi: 10.1002/anie.201612299. Epub 2017 Mar 2.

Authors

Alicia Casitas¹, Julian A Rees^{2

3}, Richard Goddard¹, Eckhard Bill², Serena DeBeer^{2

4}, Alois Fürstner¹

Affiliations

¹ Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
² Max-Planck-Institut für Chemische Energiekonversion, 45470, Mülheim/Ruhr, Germany.
³ Department of Chemistry, University of Washington, Box 351700, Seattle, WA, 98195-1700, USA.
⁴ Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853, USA.

PMID: 28251752
DOI: 10.1002/anie.201612299

Abstract

The formation of the high-valent iron complex [Fe(cyclohexyl)₄ ] from Fe^II under reducing conditions is best explained by disproportionation of a transient organoiron intermediate which is driven by dispersive forces between the cyclohexyl ligands and the formation of short and strong Fe-C bonds. The (meta)stability of this diamagnetic complex (S=0) is striking if one considers that it has empty d-orbitals at its disposal and contains, at the same time, no less than twenty H-atoms available for either α- or β-hydride elimination.

Keywords: London dispersive forces; hydride elimination; iron; transition metal complexes.

Publication types

Research Support, Non-U.S. Gov't