Surface electrostatic potentials of halogenated methanes as indicators of directional intermolecular interactions

1992/03/14 by Tore Brinck, Jane S. Murray, Peter Politzer · 440 citations
Chemistry · Pharmacology, Toxicology and Pharmaceutics · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Alkyl #Benzene #Chemical physics #Chemistry #Computational chemistry #Electrophile #Fluorine #Fluorine in Organic Chemistry #Halogen #Halogen bond #Hexafluorobenzene #Intermolecular force #Lone pair #Molecular Spectroscopy and Structure #Molecule #Nucleophile #Organic chemistry #Pyridine #Tetrahydrofuran

paper · doi:10.1002/qua.560440709

published in International Journal of Quantum Chemistry 44(S19), 57-64 (Wiley)

openalex publication_date 1992/03/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

Using an ab initio self-consistent-field molecular orbital approach, we have computed 6-31G*//STO-3G* electrostatic potentials for CH3F, CF4, CH3Cl, CCl4, CH3Br, and CBr4. It is demonstrated that the potentials along the carbon–halogen bonds of these systems can explain the observed directional preferences of the halogens' intermolecular interactions. Our surface potentials for the chlorinated and brominated molecules favor the observed “side-on” and “head-on” interactions with electrophiles and nucleophiles, respectively, of CCl and CBr in crystals, whereas the potentials of CH3F and CF4 are indicative of fluorine interacting only with electrophiles, as is found experimentally. The strongly positive potentials at the ends of the chlorines and bromines in CCl4 and CBr4 are consistent with complexes that these form with electron donors, e.g., the π regions of benzene and p-xylene and the lone pairs of pyridine and tetrahydrofuran. © 1992 John Wiley & Sons, Inc.

Cited by

• σ‐Hole bonding and hydrogen bonding: Competitive interactions
• Hydride‐Triel Bonds
• σ-Holes, π-holes and electrostatically-driven interactions
• Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity
• Halogen-like Behavior of Gold: Can Gold Form Pseudo-Halogen Bonds?
• Halogen bonding: the σ-hole
• An overview of halogen bonding
• Halogen bonding and the design of new materials: organic bromides, chlorides and perhaps even fluorides as donors
• Expansion of the σ-hole concept
• Modelling water isotopes for an improved interpretation of climate proxy records
• Blue shifts vs red shifts in σ-hole bonding
• Theoretical description of halogen bonding - an insight based on the natural orbitals for chemical valence combined with the extended-transition-state method (ETS-NOCV). [europepmc]
• ETS-NOCV description of σ-hole bonding. [europepmc]
• The Halogen Bond. [europepmc]
• Theoretical Study of Intramolecular Interactions in Peri-Substituted Naphthalenes: Chalcogen and Hydrogen Bonds. [europepmc]
• Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds. [europepmc]
• Halogen and Hydrogen Bonding Interplay in the Crystal Packing of Halometallocenes. [europepmc]
• Cooperative Effects in Weak Interactions: Enhancement of Tetrel Bonds by Intramolecular Hydrogen Bonds. [europepmc]
• Theoretical Description of R-X⋯NH 3 Halogen Bond Complexes: Effect of the R Group on the Complex Stability and Sigma-Hole Electron Depletion. [europepmc]
• In Situ Assessment of Intrinsic Strength of X-I⋯OA-Type Halogen Bonds in Molecular Crystals with Periodic Local Vibrational Mode Theory. [europepmc]
• Unconventional Type III Halogen···Halogen Interactions: A Quantum Mechanical Elucidation of σ-Hole···σ-Hole and Di-σ-Hole Interactions. [europepmc]
• Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4'-Bipyridine Derivatives. [europepmc]
• Supramolecular Halogen Bonds in Asymmetric Catalysis. [europepmc]
• Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons. [europepmc]
• Electrostatic Potential Topology for Probing Molecular Structure, Bonding and Reactivity. [europepmc]
• A Combined Experimental/Quantum-Chemical Study of Tetrel, Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules. [europepmc]
• Solving the enigma of weak fluorine contacts in the solid state: a periodic DFT study of fluorinated organic crystals. [europepmc]
• Insight into trifluoromethylation - experimental electron density for Togni reagent I. [europepmc]
• Transition Metal Catalysis Controlled by Hydrogen Bonding in the Second Coordination Sphere. [europepmc]
• Stereoselective Processes Based on σ-Hole Interactions. [europepmc]
• The Distance between Minima of Electron Density and Electrostatic Potential as a Measure of Halogen Bond Strength. [europepmc]
• Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control. [europepmc]
• The Formation of σ-Hole Bonds: A Physical Interpretation. [europepmc]
• The Halogen Bond to Ethers - Prototypic Molecules and Experimental Electron Density. [europepmc]
• Anion transporters based on halogen, chalcogen, and pnictogen bonds: towards biological applications. [europepmc]
• When CuCl 4 2- and CuBr 4 2- Form Anion···Anion Networks Assembled via Cu···Cl/Br Regium Bonds. [europepmc]

Related

• Influence of Three-Body Effects on Halogen Bonding
• Halogen Bond Structure and Dynamics from Molecular Simulations
• Polyhalogenated Molecules in the Polarizable Ellipsoidal Force Field Model
• Parameter Estimation by Density Functional Theory for a Lattice-gas Model of Br and Cl Chemisorption on Ag(100)
• The Effect of Off-Center σ-Hole on the Atom-Centered Partial Charges in Halogenated Molecules