Weak Interactions Break Strong Bonds: Noncovalent Complexes of H–X with N-Heterocycles DOI

Jagadeesan Sreelakshmy,

Kalarikkal B. Indulekha,

Eapen Thomas

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: May 21, 2025

The phenomenon of positive cooperativity in noncovalent complexes, arising from electron donor-acceptor (eDA) interactions and subsequent reorganization, has been investigated by using density functional theory (DFT) at the ωB97XD/6-311 + G(3df,2pd) level. study focuses on interaction various nitrogen- oxygen-containing heterocycles with HF HCl molecules. formation dimer complexes leads to flow nitrogen lone pair hydrogen halide, enhancing halogen atom, as made evident molecular electrostatic potential (MESP) analysis. introduction additional HX molecules induces cooperativity, strengthening N···H ultimately facilitating spontaneous H-X bond cleavage stable ion pairs. Substituent effects positional isomerism substituted pyridines reveal that electron-donating groups─especially ortho position─markedly enhance activation via neighboring group effects. Cooperative enhancement is also demonstrated higher-order clusters (trimers pentamers), particularly for stronger H-F bond, which requires greater synergy cleave. studies O-heterocycles highlighted impact electronegativity extent requirement cooperative achieve cleavage. ΔVn(Cl) MESP parameter shows a strong correlation energy, serving predictive descriptor activation. These findings provide valuable insights into remarkable ability weak facilitate breaking bonds, offering broad implications catalysis, design, strategies.

Language: Английский

Thiazolidine Derivatives as Promising Prostate Cancer Agents: Design, Synthesis, In Vitro Evaluation, DFT, ADME, POM, Docking, and Toxicity Studies DOI

Hamsa Hussein Al-Hujaj,

Ahmed A. Majed,

Qeaser R. Abdalzahra

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142544 - 142544

Published: April 1, 2025

Language: Английский

Citations

0
Unveiling the Hypervalent Electronic Structure of Main Group Zwitterions: Ylides or Ylenes? A DFT Study DOI

Mathew Saumini,

Cherumuttathu H. Suresh

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(13)

Published: May 14, 2025

ABSTRACT This study uses density functional theory ( DFT ) calculations at the M06 ‐ 2X /6–311 + G(d,p) level to explore potential of main group non‐metals (X = O, N, S, P) form hypervalent ylides R m X – YR n −2 − ). Substituent effects alkoxy, alkyl, phenyl, H, NH 2 , NMe halogens) on stability these and their neutral counterparts (R m− 1 −1 are analyzed across various → Y bonding scenarios. Fluorine‐substituted (e.g., N h O /F S P / OMe exhibited highest compared forms. Bond length Wiberg bond order analyses reveal significant double character X–Y bond, confirming structure molecule. Molecular electrostatic MESP analysis shows reduced charge separation delocalized electron molecule, supporting a ylene resonance These findings provide insights into electronic molecules, aiding design novel compounds.

Language: Английский

Citations

0
Weak Interactions Break Strong Bonds: Noncovalent Complexes of H–X with N-Heterocycles DOI

Jagadeesan Sreelakshmy,

Kalarikkal B. Indulekha,

Eapen Thomas

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: May 21, 2025

The phenomenon of positive cooperativity in noncovalent complexes, arising from electron donor-acceptor (eDA) interactions and subsequent reorganization, has been investigated by using density functional theory (DFT) at the ωB97XD/6-311 + G(3df,2pd) level. study focuses on interaction various nitrogen- oxygen-containing heterocycles with HF HCl molecules. formation dimer complexes leads to flow nitrogen lone pair hydrogen halide, enhancing halogen atom, as made evident molecular electrostatic potential (MESP) analysis. introduction additional HX molecules induces cooperativity, strengthening N···H ultimately facilitating spontaneous H-X bond cleavage stable ion pairs. Substituent effects positional isomerism substituted pyridines reveal that electron-donating groups─especially ortho position─markedly enhance activation via neighboring group effects. Cooperative enhancement is also demonstrated higher-order clusters (trimers pentamers), particularly for stronger H-F bond, which requires greater synergy cleave. studies O-heterocycles highlighted impact electronegativity extent requirement cooperative achieve cleavage. ΔVn(Cl) MESP parameter shows a strong correlation energy, serving predictive descriptor activation. These findings provide valuable insights into remarkable ability weak facilitate breaking bonds, offering broad implications catalysis, design, strategies.

Language: Английский

Citations

0