Abstract
We have quantum chemically investigated the origin of the atypical blueshift of the H−C bond stretching frequency in the hydrogen-bonded complex X−•••H3C−Y (X, Y=F, Cl, Br, I), as compared to the corresponding redshift occurring in Cl−•••H3N and Cl−•••H3C−H, using relativistic density functional theory (DFT) at ZORA-BLYP-D3(BJ)/QZ4P. Previously, this blueshift was attributed, among others, to the contraction of the H−C bonds as the H3C moiety becomes less pyramidal. Herein, we provide quantitative evidence that, instead, the blueshift arises from a direct and strong X−•••C interaction of the HOMO of A− with the backside lobe on carbon of the low-lying C−Y antibonding σ* LUMO of the H3C−Y fragment. This X−•••C bond, in essence a tetrel bond, pushes the H atoms towards a shorter H−C distance and makes the H3C moiety more planar. The blueshift may, therefore, serve as a diagnostic for tetrel bonding.
| Original language | English |
|---|---|
| Article number | e202300480 |
| Pages (from-to) | 1-9 |
| Number of pages | 9 |
| Journal | ChemPhysChem |
| Volume | 25 |
| Issue number | 1 |
| Early online date | 21 Oct 2023 |
| DOIs | |
| Publication status | Published - 2 Jan 2024 |
Bibliographical note
Publisher Copyright:© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.
Funding
We thank the Netherlands Organization for Scientific Research (NWO) for support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. . We thank the Netherlands Organization for Scientific Research (NWO) for support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative
| Funders | Funder number |
|---|---|
| SURF Cooperative | |
| Nederlandse Organisatie voor Wetenschappelijk Onderzoek |
Keywords
- Bond theory
- Density functional calculations
- Energy decomposition analysis
- Hydrogen bonds
- Noncovalent interactions