The complexes formed between TX-ZX (T = C, Si, Ge; Z = P, As, Sb; X = F, Cl) and NH were studied at the MP2/aug-cc-pVTZ(PP) level. For each TX-ZX, two types of complex were obtained. For CX-ZX, NH is inclined to approach the σ-hole on the Z atom, forming a pnicogen bond. For TX-ZX (T = Si and Ge), however, the base favors engaging in a tetrel bond with the σ-hole on the T atom although the corresponding pnicogen-bonded complex is also stable. When NH approaches the CX terminal of CX-ZX, weak interactions are observed that may be classified as van der Waals interactions. The relative stability of both types of complexes is not affected by the substituent X. The tetrel bond is very strong and the largest interaction energy is up to -144 kJ mol. Dispersion is dominant in the weak van der Waals complexes, while tetrel- and pnicogen-bonded complexes are dominated by electrostatic interactions, with comparable contributions from polarization.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1007/s00894-018-3732-6 | 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 PDFSimple carbenes as hydrogen bond acceptors: determination of nucleophilicities and reduced nucleophilicities.
Phys Chem Chem Phys
January 2025
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
Nucleophilicities for a range of simple carbene molecules acting as hydrogen bond acceptors B in forming complexes B⋯HX are reported. The carbenes chosen to fulfil the roles of a Lewis base are B = RM, -(CH)M, HCCM and two N-heterocyclic carbenes, where M is one of the group 14 tetrel atoms, C, Si, Ge or Sn and R = H, CH, and F. All the carbenes but CH have a singlet electronic ground state.
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 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!