NX⋯Y halogen bonds. Comparison with NH⋯Y H-bonds and CX⋯Y halogen bonds

Nepal, Binod; Scheiner, Steve

doi:10.1039/c6cp03771b

Cited by 20 publications

(19 citation statements)

References 82 publications

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“…Such DFT theoretical calculations have been already successfully used to investigate environment effects on the I-adducts. 15,21 In addition, similar calculations have also shown to provide charge density distributions very comparable with those experimentally determined from high-resolution low-temperature single-crystal X-ray diffraction data. 22 The NSac-X and X and for the donor/acceptor fragments with X belonging to one or another, are also given in Table 2.…”

Section: Theoretical Investigationssupporting

confidence: 62%

Toward a reverse hierarchy of halogen bonding between bromine and iodine

et al. 2017

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We compare here the halogen bond characteristics of bimolecular adducts involving either N-bromo- or N-iodosaccharin as strong halogen bond donors, with 4-picoline as a common XB acceptor. In the NBSac·Pic system, the bromine atom of NBSac is displaced toward the picoline, almost at a median position between the two nitrogen atoms, N and N', with NBr and BrN' distances at 2.073(6) and 2.098(6) Å respectively. This extreme situation contrasts with the analogous iodine derivative, NISac·Pic, where the N-I and IN' distances amount to 2.223(4) and 2.301(4) Å respectively. Periodic DFT calculations, and molecular calculations of adducts (PBEPBE-D2 aug-cc-pVTZ) either at the experimental frozen geometry or with optimization of the halogen position, indicate a more important degree of covalency (i.e. shared-shell character) in the adduct formed with the bromine atom. A stronger charge transfer to the picoline is also found for the bromine (+0.27 |e|) than for the iodine (+0.18 |e|) system. This inversion of halogen bond strength between I and Br finds its origin in the strong covalent character of the interaction in these adducts, in line with the strength of covalent N-Br and N-I bonds. Detailed characterization of the critical points (CPs) of the L(r) = -∇ρ(r) function along bonding directions has permitted the adducts to be distinguished and they can be respectively described as "neutral" NISac/Pic and "intermediate" NSac/Br/Pic, the latter with Br being close to formal equivalent NBr and BrN' interactions but still more associated to the XB donor than to the picoline, as indicated by the topological and energetic properties of the ρ(r) function at the bond critical points (BCPs).

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Section: Theoretical Investigationssupporting

confidence: 62%

Toward a reverse hierarchy of halogen bonding between bromine and iodine

et al. 2017

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“…[68,69] This basis set and functional have been applied previously to similar sorts of systems to good effect. [14,[33][34][35][70][71][72][73][74][75] Relativistic effects are expected to be most significant for atoms below the third row of the periodic table. Minima on each potential energy surface were assured by the absence of any negative frequencies.…”

Section: Methodsmentioning

confidence: 99%

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

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102

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The interactions of halides with a number of bipodal receptors were examined by quantum chemical methods. The receptors were based on a dithieno thiophene framework in which two S atoms can engage in a pair of chalcogen bonds with a halide. These two S atoms were replaced by P and As atoms to compare chalcogen with pnicogen bonding, and by Ge which engages in tetrel bonds with the receptor. Zero, one, and two O atoms were added to the thiophene S atom which is not directly involved in the interaction with the halides. Fluoride bound the most strongly, followed by Cl , Br , and I , respectively. Replacing S by the pnicogen bonds of P strengthened the binding, as did moving down to As in the third row of the periodic table. A further large increment is associated with the switch to the tetrel bonds of Ge. Even though the thiophene S atom is remote from the binding site, each additional O atom added to it raises the binding energy, which can be quite large, as much as 63 kcal mol for the Ge⋅⋅⋅F interaction. The receptors have a pronounced selectivity for F over the other halides, as high as 27 orders of magnitude. The data suggest that incorporation of tetrel atoms may lead to new and more powerful halide receptors.

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“…Some of the complexes presented herein (Table 1) have been analyzed in previous studies. These are the FCl···NH 3 , [44][45][46][47][48][49][50][51][52] FBr···NH 3 , [52] SeFH···NH 3 , [53,54] PFH 2 ···NH 3 , [55] SFH···C 2 H 2 , [56] FCl···C 2 H 2 , [46][47][48][57][58][59] PFH 2 ···C 2 H 2 , [60] and Si/GeFH 3 ···NH 3 [61,62] complexes. However,c alculations were performed at different levels and these studies concerned rather narrow types of interaction;h erein the same high level of calculation was applied for the varioust ypes of s-hole bond.…”

Section: Lewisa Cidmentioning

confidence: 99%

Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Grabowski

Sokalski

2017

ChemPhysChem

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Representative Lewis acid-Lewis base complexes linked by tetrel, pnicogen, chalcogen, and halogen bonds have been studied within the quantum theory of atoms in molecules (QTAIM) approach and the hybrid variation-perturbation theory (HVPT) to analyze possible relationships between these σ-hole dimers. Results obtained at the MP2/aug-cc-pVTZ level indicate numerous correlations similar to hydrogen-bonded systems.

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NX⋯Y halogen bonds. Comparison with NH⋯Y H-bonds and CX⋯Y halogen bonds

Cited by 20 publications

References 82 publications

Toward a reverse hierarchy of halogen bonding between bromine and iodine

Toward a reverse hierarchy of halogen bonding between bromine and iodine

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

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