Next Article in Journal
Structural Characterization of the Lactobacillus Plantarum FlmC Protein Involved in Biofilm Formation
Previous Article in Journal
Synthesis, Structural and Thermal Studies of 3-(1-Benzyl-1,2,3,6-tetrahydropyridin-4-yl)-5-ethoxy-1H-indole (D2AAK1_3) as Dopamine D2 Receptor Ligand
Previous Article in Special Issue
Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study
Article Menu
Issue 9 (September) cover image

Export Article

Open AccessArticle
Molecules 2018, 23(9), 2250; https://doi.org/10.3390/molecules23092250

An Ab Initio Investigation of the Geometries and Binding Strengths of Tetrel-, Pnictogen-, and Chalcogen-Bonded Complexes of CO2, N2O, and CS2 with Simple Lewis Bases: Some Generalizations

1
Instituto de Química Médica (IQM-CSIC), Juan de la Cierva, 3, E-28006 Madrid, Spain
2
School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK
*
Authors to whom correspondence should be addressed.
Received: 20 August 2018 / Revised: 29 August 2018 / Accepted: 30 August 2018 / Published: 4 September 2018
(This article belongs to the Special Issue Tetrel Bonds)
Full-Text   |   PDF [2496 KB, uploaded 4 September 2018]   |  

Abstract

Geometries, equilibrium dissociation energies (De), and intermolecular stretching, quadratic force constants (kσ) are presented for the complexes B⋯CO2, B⋯N2O, and B⋯CS2, where B is one of the following Lewis bases: CO, HCCH, H2S, HCN, H2O, PH3, and NH3. The geometries and force constants were calculated at the CCSD(T)/aug-cc-pVTZ level of theory, while generation of De employed the CCSD(T)/CBS complete basis-set extrapolation. The non-covalent, intermolecular bond in the B⋯CO2 complexes involves the interaction of the electrophilic region around the C atom of CO2 (as revealed by the molecular electrostatic surface potential (MESP) of CO2) with non-bonding or π-bonding electron pairs of B. The conclusions for the B⋯N2O series are similar, but with small geometrical distortions that can be rationalized in terms of secondary interactions. The B⋯CS2 series exhibits a different type of geometry that can be interpreted in terms of the interaction of the electrophilic region near one of the S atoms and centered on the C axis of CS2 (as revealed by the MESP) with the n-pairs or π-pairs of B. The tetrel, pnictogen, and chalcogen bonds so established in B⋯CO2, B⋯N2O, and B⋯CS2, respectively, are rationalized in terms of some simple, electrostatically based rules previously enunciated for hydrogen- and halogen-bonded complexes, B⋯HX and B⋯XY. It is also shown that the dissociation energy De is directly proportional to the force constant kσ, with a constant of proportionality identical within experimental error to that found previously for many B⋯HX and B⋯XY complexes. View Full-Text
Keywords: intermolecular force constants; dissociation energies; CCSD(T)/aug-cc-pVTZ calculations; non-covalent bonds intermolecular force constants; dissociation energies; CCSD(T)/aug-cc-pVTZ calculations; non-covalent bonds
Figures

Graphical abstract

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

SciFeed

Share & Cite This Article

MDPI and ACS Style

Alkorta, I.; Legon, A.C. An Ab Initio Investigation of the Geometries and Binding Strengths of Tetrel-, Pnictogen-, and Chalcogen-Bonded Complexes of CO2, N2O, and CS2 with Simple Lewis Bases: Some Generalizations. Molecules 2018, 23, 2250.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top