Comparative Study of the Thermal Stabilities of the Experimentally Known High-Valent Fe(IV) Compounds Fe(1-norbornyl)4 and Fe(cyclohexyl)4.

The high stability of the experimentally known homoleptic 1-norbornyl derivative (nor)4Fe of iron in the unusual +4 oxidation state is a consequence of the high reaction barriers of the singlet or triplet potential surfaces constrained by the global dispersion attraction and the great steric demands of the norbornyl groups. The much more limited stability of the corresponding cyclohexyl derivative (cx)4Fe may result from the conical intersection between the singlet potential surface and the quintet spin potential surface arising from the weaker dispersion attraction and the reduced steric effect of the cyclohexyl groups relative to the 1-norbornyl groups. In contrast, the high stability of the likewise experimentally known (cx)4M (M = Ru or Os) structures results from the larger ligand field splitting (Δ) of the d-orbital energies for the second and third-row transition metals ruthenium and osmium relative to that of the first-row transition metal iron. The cyclohexyl derivative (cx)4Fe is predicted to be reactive toward carbon monoxide to insert CO into up to two Fe-C bonds. However, the dispersion effect as well as the much larger size of the 1-norbornyl substituents prevents similar reactivity of (nor)4Fe with carbon monoxide.