Startseite O–Li⋯O and C–Li⋯C lithium bonds in small closed shell and open shell systems as analogues of hydrogen bonds
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O–Li⋯O and C–Li⋯C lithium bonds in small closed shell and open shell systems as analogues of hydrogen bonds

  • Dávid Vrška ORCID logo , Miroslav Urban ORCID logo , Pavel Neogrády und Michal Pitoňák ORCID logo EMAIL logo
Veröffentlicht/Copyright: 14. August 2025
Pure and Applied Chemistry
Aus der Zeitschrift Pure and Applied Chemistry

Abstract

Hydrogen bonded complexes and their lithium bonded analogues are investigated using DFT CAM-B3LYP quantum chemistry methods. The accuracy of DFT is verified by CCSD(T) calculations. Structures, binding energies, and Hirshfeld charge and spin densities for several charged closed shell and neutral open shell oxygen-containing complexes with O–H⋯O and O–Li⋯O bonds are compared. We also studied H-bonded and Li-bonded C–H⋯C and C–Li⋯C complexes in which the hydrogen and lithium bond donor and bond acceptor act through carbon-containing groups. Attention is paid to the bonding character in the model (H3C)2–CH–Li–CH–(CH3)2 (diisopropyllithium) doublet. Its binding energy with respect to the isopropyllithium and the isopropyl radical is −45 kJ/mol. The potential energy curve for the transfer of the lithium atom between the two carbon atoms shows double minima with a barrier of 11 kJ/mol. The Hirshfeld charge and spin density analysis shows that the charge transfer from the isopropyl radical to the isopropyllithium molecule occurs, and in combination with electrostatic interaction and (about 25 %) dispersion contribution are responsible for the formation of the Li-bonded (H3C)2–CH–Li–CH–(CH3)2 complex.

Keywords: C–Li–C bond; diisopropyllithium; double-well potential; H-bond; Li-bond; O–Li–O bond
Corresponding author: Michal Pitoňák, Faculty of Natural Sciences, Department of Physical and Theoretical Chemistry, Comenius University in Bratislava, Ilkovičova 6, SK-84215 Bratislava, Slovakia; and Computing Centre, Centre of Operations of the Slovak Academy of Sciences, Dúbravská cesta 9, SK-84535 Bratislava, Slovakia, e-mail:
Article note: A collection of invited papers to celebrate the UN’s proclamation of 2025 as the International Year of Quantum Science and Technology.

Funding source: Agentúra na Podporu Výskumu a Vývoja

Award Identifier / Grant number: APVV-20-0127

Funding source: Agentúra Ministerstva Školstva, Vedy, Výskumu a Športu SR

Award Identifier / Grant number: VEGA 1/0254/24

Acknowledgments

The authors thank Martin Ošťadnický for his help with the visualization of some of the results, Daniel Kráľ for his versatile technical support, and also Michal Májek for fruitful discussions. The research used the computational resources of the high performance computing system at Comenius University in Bratislava (https://uniba.sk/en/HPC-Clara).

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: This study was funded by the Slovak Research and Development Agency under Grant Agreement APVV-20-0127 and the VEGA grant 1/0254/24 from the Ministry of Education, Research, Development and Youth of the Slovak Republic.

  7. Data availability: All data generated or analyzed during this study are included in this published article [and its Supplementary information files].

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/pac-2025-0532).

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Received: 2025-06-02
Accepted: 2025-07-18
Published Online: 2025-08-14

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https://doi.org/10.1515/pac-2025-0532
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C–Li–C bond; diisopropyllithium; double-well potential; H-bond; Li-bond; O–Li–O bond
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