A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Abstract

The characteristics and nature of the halogen bonding in a series of BÁÁÁXY (B = H 2 S, H 2 CS, (CH 2 ) 2 S; XY = ClF, Cl 2 , BrF, BrCl, Br 2 ) complexes were analyzed by means of the quantum theory of ''atoms in molecules'' (QTAIM) and ''natural bond orbital'' (NBO) methodology at the second-order Møller-Plesset (MP2) level. Electrostatic potential, bond length, interaction energy, topological properties of the electron density, the dipole moment, and the charge transfer were investigated systematically. For the same electron donor, the interaction energies follows the BÁÁÁBrF [ BÁÁÁClF [ BÁÁÁBrCl [ BÁÁÁBr 2 [ BÁÁÁCl 2 [ BÁÁÁClBr order. For the same electron acceptor, the interaction energies increase in the sequence of H 2 S, H 2 CS, and (CH 2 ) 2 S. Topological analyses show these halogen bonding interactions belong to weak interactions with an electrostatic nature. It was found that the strength of the halogen-bonding interaction correlates well with the electrostatic potential associated with halogen atom and the amount of charge transfer from sulfides to dihalogen molecules, indicating that electrostatic interaction plays an important role in these halogen bonds. Charge transfer is also an important factor in the halogen bonds involved with dihalogen molecules.Keywords Halogen bond Á Topological analysis of electron density Á Natural bond orbital analysis Á Electrostatic interaction Á Charge transfer

Theoretical study of the interaction of fluorinated dimethyl ethers and the ClF and HF molecules. Comparison between halogen and hydrogen bonds

“…Let us also mention that the interaction between DME and HF has been investigated some time ago by the matrix isolation technique . It should also be noticed that the interaction between FCl and several Lewis bases of different nature such as H 2 O, NH 3 , H 2 S, PH 3 , OH − , Br − has been investigated by theoretical methods but as far as we know, the interaction between the FDMEs and ClF has not been systematically investigated. The fluorinated derivatives of DME considered in present study are CH 3 OCH 3 , CH 2 FOCH 3 , CHF 2 OCH 3 , CH 2 FOCH 2 F, CF 3 OCH 3 , CH 2 FOCHF 2 , and CHF 2 OCHF 2 .…”

Electron density Laplacian and halogen bonds

“…This space region is thus prone to interact with the lone electron pair(s) carried by the partner. Recently, a similar analysis (also valid for homologous noncovalent bonds) has been proposed using, as the primary physical observable, the electron density Laplacian ∇ 2 ρ(� r) [25][26][27][28] instead of MEP, leading to the so-called lump-hole interaction paradigm [29]: the electron-deficient region at the periphery of the halogen atom is then viewed as a "hole" that can be filled by the electron-rich Lewis base's lump. Indeed, it is very well known that charge depletion areas are easily characterized by positive ∇ 2 ρ(� r) values, while charge concentration occurs when ∇ 2 ρ(� r) is negative.…”

Interplay of thermochemistry and Structural Chemistry, the Journal (volume 22, 2011, issues 1–3) and the discipline

“…Zhang et al [155] used QTAIM and NBO methods to study intramolecular interactions between sulfides (H 2 S, H 2 CS, (CH 2 ) 2 S) with dihalogen molecules (Cl 2 , Br 2 , ClF, BrF, BrCl). For the same electron donor, the interaction energies follow the BÁÁÁBrF [ BÁÁÁClF [ BÁÁÁBrCl [ BÁÁÁBr 2 [ BÁÁÁCl 2 [ BÁÁÁClBr order and for the same electron acceptor H 2 S, H 2 CS, and (CH 2 ) 2 S order.…”