Laser spectroscopic and computational insights into unexpected structural behaviours of sandwich complexes upon ionization

Transition-metal sandwich complexes play key roles in various fields such as fundamental and applied chemistry; many of their unique properties arise from their ability to form stable or reactive ions. The first mass-analyzed threshold ionization (MATI) spectra of mixed sandwich compounds, (Ch)(Cp)Cr and (Cot)(Cp)Ti (Ch = eta, Cp = eta, Cot = eta), presented in this work provide an extremely accurate description of the electron detachment. The ionization energies of the neutrals and stabilization energies of the metal-ligand interactions upon ionization are derived from the MATI data with an accuracy of 0.0006 eV. In combination with DFT calculations, laser threshold ionization spectroscopy reveals surprisingly different structural variations accompanying the detachment of the non-bonding d electron from the sandwich molecules. The geometry of (Ch)(Cp)Cr remains practically unchanged while the ionization of (Cot)(Cp)Ti causes a noticeable shortening of the inter-ring distance, similar to that resulting from the ionization of a typical antibonding orbital. Electron density analysis throws light on the nature of these amazing effects.

Automated summary

Transition-metal sandwich complexes play important roles in various fields due to their ability to form stable or reactive ions. This study presents accurate descriptions of electron detachment in mixed sandwich compounds through mass-analyzed threshold ionization (MATI) spectra. Laser threshold ionization spectroscopy, combined with DFT calculations, reveals different structural variations upon detachment of the non-bonding d electron from the sandwich molecules, shedding light on the nature of these effects.