Probing Electronic Effects in Tridentate Copper(I) Complexes by CIVP Spectroscopy

Ligand electronic effects play an important role in catalysis, where small changes to ligand structure can bring about large changes in catalytic activity. Therefore, accurate experimental quantification of ligand electronic properties plays a crucial role in understanding and tuning chemical reactivity. In this work, we used cryogenic ion vibrational predissociation (CIVP) spectroscopy to experimentally quantify electronic effects in terpyridine ligands, as simple model systems, by measuring CIVP spectra of their copper complexes tagged by N-2 molecules. We used the N-2 stretching vibration as a reporter chromophore to probe electronic effects of the investigated ligands and employed quantum chemical calculations to better understand how different substituents influence the vibrational frequencies of the stretching vibration of the chromophore. Our data show that the electronic character, as well as position and number of substituents, can affect the N? N vibrational frequency, and that the N?N bond serves as a sensitive probe for electronic and steric effects.

Automated summary

Ligand electronic effects have a significant impact in catalysis, and experimental quantification of these effects can provide insights into chemical reactivity. In this study, cryogenic ion vibrational predissociation (CIVP) spectroscopy was used to measure the electronic effects of terpyridine ligands. The results showed that the electronic character and substituents of the ligands influenced the vibrational frequencies of the reporter chromophore.