In this study, fifty-one iconic tetrel bonding complexes were studied using the block localized wave function (BLW) method which can derive the self-consistent wavefunction for an electron-localized (diabatic) state where charge transfer is strictly deactivated. Energy decompositions based on the BLW method (BLW-ED in short) show that the frozen energy, which is mostly composed of the Pauli repulsion and electrostatic components, plays the dominating role in thirty-one out of these fifty-one systems. A further quantitative study of electrostatic potential (ESP) was carried out by analyzing the variation of ESP along the binding direction for each monomer. In general, a Lewis base with the stronger ESP leads to higher stabilizing frozen and polarization energies. In addition, the relative strengths for complexes constructed with different carbon group elements are also examined qualitatively using the ESP model. The positive contribution of the charge transfer interaction is confirmed by both the BLW-ED results and the weakening of bond strengths after the charge transfer interaction is disabled. Finally, by replacing all atoms of a monomer with σ-holes (Lewis acid) with empirical point charges, attractive electrostatic interaction was observed in all cases, providing us a simple electrostatic explanation for the tetrel bonding, though the anisotropy of electron density associated with the σ-holes is unconsidered.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c9cp01710k | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ability of the Spectroscopic Properties of the P═Se Bond of a Base to Assess Noncovalent Bond Strength.
J Phys Chem A
January 2025
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, United States.
The viability of the P═Se bond to serve as a monitor of the strength of a noncovalent bond was tested in the context of the (CH)PSe molecule. Density functional theory (DFT) computations paired this base with a collection of Lewis acids that spanned hydrogen, halogen, chalcogen, pnicogen, and tetrel bonding interactions and covered a wide range of bond strengths. A very strong linear correlation was observed between the interaction energy and the nuclear magnetic resonance (NMR) J(PSe) coupling constant, which could serve as an accurate indicator of bond strength.
View Article and Find Full Text PDFCorrelation between Noncovalent Bond Strength and Spectroscopic Perturbations within the Lewis Base.
J Phys Chem A
December 2024
Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, Wrocław 50-370, Poland.
Article Synopsis
- * The study evaluated interaction energy through comparisons with spectroscopic data, geometric properties, and other factors to uncover correlations, particularly focusing on the C═O stretching frequency and nuclear magnetic resonance changes.
- * While the interaction energy can be estimated from experimental measurements, standard AIM measurements correlate less effectively, and the σ-hole depth on the Lewis acid does not strongly relate to bond strength due to the limitations of electrostatic metrics.
Carbon-Bromide Bond Activation by Bidentate Halogen, Chalcogen, Pnicogen, and Tetrel Bonds.
J Phys Chem A
December 2024
College of Chemistry and Materials Science, Hebei Key Laboratory of Inorganic Nano-Materials, Hebei Normal University, Shijiazhuang 050024, China.
Halogen, chalcogen, pnictogen, and tetrel bonds in organocatalysis have gained noticeable attention. In this work, carbon-bromide bond activation in the Ritter reaction by bidentate imidazole-type halogen, chalcogen, pnicogen, and tetrel bond donors was studied by density functional theory. All of the above four kinds of catalysts exhibited excellent catalytic performance.
View Article and Find Full Text PDFTwo-Factor Rule for Distinguishing the Covalent and Tetrel Bonds.
Chempluschem
November 2024
Research Laboratory of Multiscale modelling of multicomponent materials, South Ural State University, 76, Lenin ave, Chelyabinsk, Russia, 454080.
Understanding and exploring the existence of a recognizable boundary between the noncovalent tetrel bond (TtB) and the coordination or weakened covalent bond are important for the bonding characterization. We have developed a simple methodology for analysing the type of bonds based on comparison of the electrostatic and total static potentials along the bond line. For the typical σ-hole noncovalent bond formed by a Tt atom in a tetrahedral molecule, we have found that the space gap between positions of the maxima of the total static potential and the negative quantity of electrostatic potential is much wider than that for the coordination bonds in a trigonal bipyramid molecular system for the Cl-Tt/Cl⋅⋅⋅Tt and N-Tt/N⋅⋅⋅Tt (Tt=C, Si, Ge) bonds in molecules and molecular complexes.
View Article and Find Full Text PDFPro stabilization in prolyl carbamates influenced by tetrel bonding interactions.
Org Biomol Chem
November 2024
Department of Chemistry, Indian Institute of Science, Bangalore, Karnataka - 560012, India.
NMR spectral and theoretical analyses of homologous prolyl carbamates reveal subtle charge transfer tetrel bonding interactions (TBIs), selectively stabilizing their Pro rotamers. These TBIs involve C-terminal-amide to N-terminal carbamate carbonyl-carbonyl (n → π* type) followed by intra-carbamate (n → σ* type) charge transfer interactions exclusively in the Pro motif. The number of TBIs and hence the Pro stability increase with increasing number of C groups at the carbamate alcohol.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!