Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Kuznetsov, Maxim L.

doi:10.3390/molecules26072083

Cited by 14 publications

(17 citation statements)

References 148 publications

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“…Further, this study experimentally demonstrated that the chlorine bonded to an electron-rich arene ligand acts as a nucleophile by donating an electron density towards the polarized chlorine coordinately bonded to the central Zn metal cation (Figure 5b). The experimental observations are recently further corroborated by several theoretical studies based on the topological analysis [52,53].…”

Section: Halogen Bondssupporting

confidence: 61%

“…It was shown that the positive electrostatic potentials above carbonyl carbon atoms in acetyl fluoride and acetamide correlate well with their relative tendencies towards nucleophilic substitution reactions, such as hydrolysis [80]. Both positive σ-holes and π-holes can be present in one molecule and their interactions with negative sites such as lone pairs and anions are highly directional [53,88,89].…”

Section: π-Holes Interactionsmentioning

confidence: 99%

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The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

et al. 2022

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The work carried out by our research group over the last couple of decades in the context of quantitative crystal engineering involves the analysis of intermolecular interactions such as carbon (tetrel) bonding, pnicogen bonding, chalcogen bonding, and halogen bonding using experimental charge density methodology is reviewed. The focus is to extract electron density distribution in the intermolecular space and to obtain guidelines to evaluate the strength and directionality of such interactions towards the design of molecular crystals with desired properties. Following the early studies on halogen bonding interactions, several “sigma-hole” interaction types with similar electrostatic origins have been explored in recent times for their strength, origin, and structural consequences. These include interactions such as carbon (tetrel) bonding, pnicogen bonding, chalcogen bonding, and halogen bonding. Experimental X-ray charge density analysis has proved to be a powerful tool in unraveling the strength and electronic origin of such interactions, providing insights beyond the theoretical estimates from gas-phase molecular dimer calculations. In this mini-review, we outline some selected contributions from the X-ray charge density studies to the field of non-covalent interactions (NCIs) involving elements of the groups 14–17 of the periodic table. Quantitative insights into the nature of these interactions obtained from the experimental electron density distribution and subsequent topological analysis by the quantum theory of atoms in molecules (QTAIM) have been discussed. A few notable examples of weak interactions have been presented in terms of their experimental charge density features. These examples reveal not only the strength and beauty of X-ray charge density multipole modeling as an advanced structural chemistry tool but also its utility in providing experimental benchmarks for the theoretical studies of weak interactions in crystals.

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Section: Halogen Bondssupporting

confidence: 61%

Section: π-Holes Interactionsmentioning

confidence: 99%

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

et al. 2022

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“…Indeed, quantitative relationships have been derived in certain classes of systems and usefully applied where the binding energy can be simply related to one or more indicators derived from these methods. For example, it is common in the literature to consider the bond critical point density as a measure of bond strength [23][24][25][26][27] and possibly even with spectroscopic perturbations. 28 In an alternate scheme, the energies of some of these bonds are sometimes assessed via a simple relationship with the potential energy density 24,[29][30][31] or other quantities extracted from AIM analysis.…”

Section: Introductionmentioning

confidence: 99%

On the reliability of atoms in molecules, noncovalent index, and natural bond orbital to identify and quantify noncovalent bonds

Scheiner

2022

J Comput Chem

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Atoms in molecules, noncovalent index, and natural bond orbital methods are commonly invoked to identify the presence of various noncovalent bonds and to measure their strength. However, there are numerous instances in the literature where these methods provide contradictory or apparently erroneous interpretations of the bonding. The range of reliability of these methods is assessed by calculations of a variety of systems, which include an H‐bond, halogen bond, π‐tetrel bond, CH··HC interaction, and a pairing of two anions. While the results appear to be meaningful for the equilibrium geometries, and those where the two subunits are progressively pulled apart, these techniques erroneously predict a progressively stronger bonding interaction as the two units are compressed and the interaction becomes clearly repulsive. The methods falsely indicate a bonding interaction in the CH··HC arrangement, and incorrectly mimic the behavior of the energy when two anions approach. These approaches are also unreliable for understanding angular deformations.

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“…The venerable H-bond − serves as the template for a host of closely related noncovalent bonds. Among these, the halogen bond is the most thoroughly characterized and utilized to date. − This bond arises when the bridging proton of the H-bond is replaced by a halogen atom, typically I, Br, or Cl. The H-bond and the halogen bond share many characteristics, such as the proclivity toward linearity and the mix of electrostatic, induction, and dispersion components that comprise the total interaction energy.…”

Section: Introductionmentioning

confidence: 99%

On the Ability of Nitrogen to Serve as an Electron Acceptor in a Pnicogen Bond

Scheiner

2021

J. Phys. Chem. A

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Whereas pnicogen atoms like P and As have been shown repeatedly to act as electron acceptors in pnicogen bonds, the same is not true of the more electronegative first-row N atom. Quantum calculations assess whether N can serve in this capacity in such bonds and under what conditions. There is a positive π-hole belt that surrounds the central N atom in the linear arrangement of NNNF, NNN-CN, and NNO, which can engage a NH3 base to form a pnicogen bond with binding energy between 3 and 5 kcal/mol. Within the context of a planar arrangement, the π-hole above the N in NO2OF, N(CN)3, and CF3NO2 is also capable of forming a pnicogen bond, the strongest of which amounts to 11 kcal/mol with NMe3 as base. In their pyramidal geometry, NF3 and N(NO2)3 engage with a base through the σ-hole on the central N, with variable binding energies between 2 and 9 kcal/mol. AIM and NBO provide somewhat different interpretations of the secondary interactions that occur in some of these complexes.

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Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Cited by 14 publications

References 148 publications

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

The Relevance of Experimental Charge Density Analysis in Unraveling Noncovalent Interactions in Molecular Crystals

On the reliability of atoms in molecules, noncovalent index, and natural bond orbital to identify and quantify noncovalent bonds

On the Ability of Nitrogen to Serve as an Electron Acceptor in a Pnicogen Bond

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