Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes.

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Previous synthesis of TiL and FeTiL complexes reported.
• Need for characterization of complete redox families of these compounds.

Purpose of the Study:

• To synthesize and characterize the complete redox families of monometallic Ti and Fe-Ti compounds.
• To elucidate the bonding and electronic structures of these complexes and their redox behavior.

Main Methods:

• Synthesis and characterization of novel Ti and Fe-Ti complexes.
• Cyclic voltammetry to study redox potentials.
• Solid-state structure determination via X-ray crystallography.
• Spectroscopic characterization (NMR, EPR, Mössbauer, XAS).
• Computational studies (DFT, TD-DFT).

Main Results:

• Synthesis of [FeTiL]+, [FeTiL]-, BrFeTiL, and [TiL]+.
• Observation of short metal-metal bonds (1.94-2.38 Å) in the [FeTiL]+/0/- series.
• Redox processes primarily Fe-based, with Fe-Ti π-bonds delocalizing electron density.

Conclusions:

• The Fe-Ti complexes exhibit unique structural and electronic properties.
• Redox activity is predominantly centered on the iron center.
• Polarized Fe-Ti π-bonds contribute to electron delocalization within the complex.