Is there a single ideal parameter for halogen-bonding-based Lewis acidity?
- Halogen-bond donors (halogen-based Lewis acids) have now found various applications in diverse fields of chemistry. The goal of this study was to identify a parameter obtainable from a single DFT calculation that reliably describes halogen-bonding strength (Lewis acidity). First, several DFT methods were benchmarked against the CCSD(T) CBS binding data of complexes of 17 carbon-based halogen-bond donors with chloride and ammonia as representative Lewis bases, which revealed M05-2X with a partially augmented def2-TZVP(D) basis set as the best model chemistry. The best single parameter to predict halogen-bonding strengths was the static σ-hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, \(\Omega\sigma\)*, has been developed through the linear combination of the \(\sigma\)-hole depth and the \(\sigma\)*(C−I) energy, which was further validated against neutral, cationic, halogen- and nitrogen-based halogen-bond donors with very good performance.
| Author: | Elric EngelageORCiDGND, Dominik ReinhardGND, Stefan M. HuberORCiDGND |
|---|---|
| URN: | urn:nbn:de:hbz:294-80898 |
| DOI: | https://doi.org/10.1002/chem.201905273 |
| Parent Title (English): | Chemistry - A European Journal |
| Publisher: | Wiley |
| Place of publication: | Weinheim |
| Document Type: | Article |
| Language: | English |
| Date of Publication (online): | 2021/05/19 |
| Date of first Publication: | 2020/03/23 |
| Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
| Tag: | Lewis acids; bond energy; density functional calculations; halogen bonding; iodine |
| Volume: | 26 |
| First Page: | 3843 |
| Last Page: | 3861 |
| Note: | Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich. |
| Institutes/Facilities: | Lehrstuhl für Organische Chemie I |
| Dewey Decimal Classification: | Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie |
| open_access (DINI-Set): | open_access |
| faculties: | Fakultät für Chemie und Biochemie |
| Licence (English): |  Creative Commons - CC BY 4.0 - Attribution 4.0 International |
