| Autor: |
Gorbachev V; ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland., Nobile AG; ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland., Tsybizova A; ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland., Chen P; ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2023 Sep 11; Vol. 62 (36), pp. 14704-14714. Date of Electronic Publication: 2023 Aug 29. |
| DOI: |
10.1021/acs.inorgchem.3c02065 |
| Abstrakt: |
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. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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