A homoleptic Fe(iv) ketimide complex with a low-lying excited state
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Updated: Jun 12, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Phoebe R Hertler1, Arturo Sauza-de la Vega2, Andrea Darù2
1Department of Chemistry and Biochemistry, University of California Santa Barbara Santa Barbara CA 93106 USA hayton@chem.ucsb.edu.
Abstract:
The reaction of 4 equiv. of Li(N[double bond, length as m-dash]C( t Bu)Ph) with FeIICl2 results in isolation of [Li(Et2O)]2[FeII(N[double bond, length as m-dash]C( t Bu)Ph)4] (1), in good yields. The reaction of 1 with 1 equiv. of I2 leads to formation of [FeIV(N[double bond, length as m-dash]C( t Bu)Ph)4] (2), in moderate yields. 57Fe Mössbauer spectroscopy confirms the Fe(iv) oxidation state of 2, and X-ray crystallography reveals that 2 has a square planar coordination geometry along with several intramolecular H⋯C interactions. Furthermore, SQUID magnetometry indicates a small magnetic moment at room temperature, suggestive of an accessible S = 1 state. Both density functional theory and multiconfigurational calculations were done to elucidate the nature of the ground state. Consistent with the experimental results, the ground state was found to be an S = 0 state with an S = 1 excited state close in energy.
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