Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion

Brammer, Lee

doi:10.1039/c7fd00199a

Cited by 165 publications

(124 citation statements)

References 70 publications

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“…There is much ongoing discussion on halogen-centered noncovalent interactions and many interesting papers [1][2][3] and reviews [4][5][6][7] have appeared. Essentially, these seek to provide a fundamental understanding of their characteristic signatures [8,9], the underlying physical chemistry involved, and the way they drive packing between molecules of interest in the development of engineered crystals [10].…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site.

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Section: Introductionmentioning

confidence: 99%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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“…As such, a simple electrostatic argument can be made for how Lewis bases then interact with the halogen, and this explains the strong geometry dependence. It has been proposed that this is just an example of a wider class of analogous interactions, with similar effects seen for chalcogens, pnictogens, and tetrels [18,[25][26][27][28]. The electrostatic potential can be calculated, and measured experimentally, confirming that the anisotropy does indeed exist [29][30][31].…”

Section: Introductionmentioning

confidence: 61%

“…These investigations discovered several striking properties, in particular the strong preference for linear geometries [12,13], where the AX•••B angle is close to 180 • , and interaction energies similar to those of hydrogen bonds [8,14]. These factors give halogen bonds a high degree of tuneability, making them ideal for use in fields ranging from crystal engineering to nanomaterials and drug design [11,[15][16][17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

A Simple Model for Halogen Bond Interaction Energies

Shaw

Hill

2019

Inorganics

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Halogen bonds are prevalent in many areas of chemistry, physics, and biology. We present a statistical model for the interaction energies of halogen-bonded systems at equilibrium based on high-accuracy ab initio benchmark calculations for a range of complexes. Remarkably, the resulting model requires only two fitted parameters, X and B—one for each molecule—and optionally the equilibrium separation, R e , between them, taking the simple form E = X B / R e n . For n = 4 , it gives negligible root-mean-squared deviations of 0.14 and 0.28 kcal mol - 1 over separate fitting and validation data sets of 60 and 74 systems, respectively. The simple model is shown to outperform some of the best density functionals for non-covalent interactions, once parameters are available, at essentially zero computational cost. Additionally, we demonstrate how it can be transferred to completely new, much larger complexes and still achieve accuracy within 0.5 kcal mol - 1 . Using a principal component analysis and symmetry-adapted perturbation theory, we further show how the model can be used to predict the physical nature of a halogen bond, providing an efficient way to gain insight into the behavior of halogen-bonded systems. This means that the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction.

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“…[9] Chalcogen bonds are secondary interactions specifically involving Group 16 elements (O,S , Se,etc. ), [10] and accordingly share several characteristics with their halogen (Group 17) and pnictogen (Group 15) bonding counterparts. [11] Chalcogen bonds have been observed in X-ray crystallographic analyses in ar ange of contexts [12] and are proposed to be significant in diastereoselective reactions of chiral organoselenium compounds,a se xemplified in pioneering work by the groups of Tomoda and Wirth among others.…”

Section: Introductionmentioning

confidence: 99%

The Importance of 1,5‐Oxygen⋅⋅⋅Chalcogen Interactions in Enantioselective Isochalcogenourea Catalysis

et al. 2020

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The importance of 1,5‐O⋅⋅⋅chalcogen (Ch) interactions in isochalcogenourea catalysis (Ch=O, S, Se) is investigated. Conformational analyses of N‐acyl isochalcogenouronium species and comparison with kinetic data demonstrate the significance of 1,5‐O⋅⋅⋅Ch interactions in enantioselective catalysis. Importantly, the selenium analogue demonstrates enhanced rate and selectivity profiles across a range of reaction processes including nitronate conjugate addition and formal [4+2] cycloadditions. A gram‐scale synthesis of the most active selenium analogue was developed using a previously unreported seleno‐Hugerschoff reaction, allowing the challenging kinetic resolutions of tertiary alcohols to be performed at 500 ppm catalyst loading. Density functional theory (DFT) and natural bond orbital (NBO) calculations support the role of orbital delocalization (occurring by intramolecular chalcogen bonding) in determining the conformation, equilibrium population, and reactivity of N‐acylated intermediates.

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Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion

Cited by 165 publications

References 70 publications

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

A Simple Model for Halogen Bond Interaction Energies

The Importance of 1,5‐Oxygen⋅⋅⋅Chalcogen Interactions in Enantioselective Isochalcogenourea Catalysis

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