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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00640065" target="_blank" >RIV/61388963:_____/25:00640065 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1515/pac-2025-0532" target="_blank" >https://doi.org/10.1515/pac-2025-0532</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1515/pac-2025-0532" target="_blank" >10.1515/pac-2025-0532</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 & ctdot,O and O-Li & ctdot,O bonds are compared. We also studied H-bonded and Li-bonded C-H & ctdot,C and C-Li & ctdot,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 is45 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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 & ctdot,O and O-Li & ctdot,O bonds are compared. We also studied H-bonded and Li-bonded C-H & ctdot,C and C-Li & ctdot,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 is45 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Pure and Applied Chemistry

ISSN

0033-4545

e-ISSN

1365-3075

Svazek periodika

97

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

16

Strana od-do

1419-1434

Kód UT WoS článku

001549968200001

EID výsledku v databázi Scopus

2-s2.0-105013853041