Halogen bonds with benzene: An assessment of DFT functionals

Forni, Alessandra; Pieraccini, Stefano; Rendine, Stefano

doi:10.1002/jcc.23507

Cited by 79 publications

(71 citation statements)

References 101 publications

(157 reference statements)

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“…This set is denoted ‘ XB51 ’. The last is a very recent analysis of halogen–π bonds by Forni et al, composed of eight dimers, with benzene as the X‐acceptor. We will term this set ‘ Xπ8 ’.…”

Section: Quantum Chemical Methodsmentioning

confidence: 99%

The many faces of halogen bonding: a review of theoretical models and methods

Wolters¹,

Schyman

Pavan³

et al. 2014

WIREs Comput Mol Sci

199

217

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Halogen bonds, the formally noncovalent interactions where the halogen acts as a Lewis acid, have brought several controversies to the theoretical world regarding its nature and components, e.g., charge transfer (CT), electrostatics, dispersion, and polarization. The debate on whether all characteristics are accounted for by electrostatics is examined, highlighting the importance of the CT and repulsive interactions. A number of strongly halogen‐bonded complexes are as covalent as metal–ligand coordination bonds. Different levels of computational methods are reviewed with the objective of finding the best accuracy/cost ratios. The unusual electronic anisotropy of the halogen donor and its interaction with a Lewis base demand specific calculation schemes. From the wave‐function theory methods, only the ones with empirical corrections (spin‐component‐scaled MP2 or CCSD, and MP2.5) are suitable when CCSD(T) is unattainable. Density functional theory functionals with a high amount of exact exchange are fast and reliable methods for halogen bonds, but double hybrids are more robust if other types of interactions are involved. Molecular mechanics methods can be useful, but only when specific corrections are added to compensate for the inability of such methods to describe CT. The most common method introduces a virtual site with a partial positive charge to account for the quantum chemical effect of the halogen bond. This methodology has been successfully applied to study protein–ligand interactions for drug design. WIREs Comput Mol Sci 2014, 4:523–540. doi: 10.1002/wcms.1189 This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Computational Biochemistry and Biophysics Theoretical and Physical Chemistry > Thermochemistry

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Section: Quantum Chemical Methodsmentioning

confidence: 99%

The many faces of halogen bonding: a review of theoretical models and methods

Wolters¹,

Schyman

Pavan³

et al. 2014

WIREs Comput Mol Sci

199

217

View full text Add to dashboard Cite

show abstract

“…In an extensive comparison of the effects of various methods and basis sets [16], this procedure has been shown to give good agreement with experimental data for C-H and N-H complexes, without requiring a correction for basis set superposition. Table 1 lists the computed interaction energies for noncovalent complexes between a variety of positive sites and the negative region potentials of several unsaturated hydrocarbons [12,[17][18][19][20][21]. The purpose of this table is simply to indicate the ranges of values; since they are from different sources, quantitative comparisons should not be made.…”

Section: Region Electrostatic Potentials and Interactions Of Unsaturamentioning

confidence: 98%

Intuitive and counterintuitive noncovalent interactions of aromatic π regions with the hydrogen and the nitrogen of HCN

Murray

Shields

Seybold

et al. 2015

Journal of Computational Science

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“…Previous calculations on related ion-pair XBs often employ the M06-2X functional, [34][35][36][37]56] which performsw ell for traditional (i.e.,n on-ion-pair) XBs [57] and interactions involving anionic electron donors. [58] On the other hand, B3LYP is undoubtedly one of the most popularf unctionals and has been used in several theoretical studies, [55,59] including ion-pair XBs.…”

Section: Introductionmentioning

confidence: 99%

Ion‐Pair Halogen Bonds in 2‐Halo‐Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects

Nunes

Costa

2017

Chemistry An Asian Journal

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The interaction of 2-halo-functionalized imidazolium derivatives (n-X ; X=Cl, Br, I) with a chloride anion through ion-pair halogen bonds (n-X⋅Cl) was studied by means of DFT and ab initio calculations. A method benchmark was performed on 2-bromo-1H-imidazol-3-ium in association with chloride (1-Br⋅Cl); MP2 yielded the best results when compared with CCSD(T) calculations. The interaction energies (ΔE) in the gas phase are high and, although the electrostatic interaction is strong owing to the ion-pair nature of the system, large X⋅⋅⋅Cl Wiberg bond orders and contributions from charge transfer (nCl- →σ*C-X) are obtained. These values drop considerably in chloroform and water; this shows that solvent plays a role in modulating the interaction and that gas-phase calculations are particularly unrealistic for experimental applications. The introduction of electron-withdrawing groups in the 4,5-positions of the imidazolium (e.g., -NO , -F) increases the halogen-bond strength in both the gas phase and solvent, including water. The effect of the substituents on the 1,3-positions (N-H groups) also depends on the solvent. The variation of ΔE can be predicted through a two-parameter linear regression that optimizes the weights of charge-transfer and electrostatic interactions, which are different in vacuum and in solvent (chloroform and water). These results could be used in the rational design of efficient chloride receptors based on halogen bonds that work in solution, in particular, in an aqueous environment.

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Halogen bonds with benzene: An assessment of DFT functionals

Cited by 79 publications

References 101 publications

The many faces of halogen bonding: a review of theoretical models and methods

The many faces of halogen bonding: a review of theoretical models and methods

Intuitive and counterintuitive noncovalent interactions of aromatic π regions with the hydrogen and the nitrogen of HCN

Ion‐Pair Halogen Bonds in 2‐Halo‐Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects

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