3 years ago

Two Exceptional Homoleptic Iron(IV) Tetraalkyl Complexes

Two Exceptional Homoleptic Iron(IV) Tetraalkyl Complexes
Serena DeBeer, Julian A. Rees, Eckhard Bill, Richard Goddard, Alois Fürstner, Alicia Casitas
The formation of the high-valent iron complex [Fe(cyclohexyl)4] from FeII 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. Let's hold together: The homoleptic and diamagnetic FeIV complex [Fe(cyclohexyl)4] is spontaneously formed under reductive conditions on treatment of FeX2 (X=Cl, acac) with excess C6H11MgCl. This unorthodox species is (meta)stable, even though the high-valent metal center has three empty d-orbitals at its disposal and is surrounded by no less than 20 hydrogen atoms available for α- or β-hydride elimination.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201612299

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