On The Nature of the Halogen Bond

Wang, Changwei; Danovich, David; Mo, Yirong

doi:10.1021/ct500422t

Cited by 250 publications

(256 citation statements)

References 79 publications

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“…Considering the classical language of a molecular orbital theory one can summarize that the "electronic" part of the CH¨¨¨HC bonding is based on both donation from the occupied σ (C-H) bonds into the empty σ*(C-H) of methyl groups as well as polarization of the C-H bonds (mixing of σ/σ*(C-H)). These stabilizing contributions (the polarization and charge transfer) are clearly mixed-at this point one can reference other important and interesting works in which the meaning of both contributions is debated in terms of non-covalent interactions [67,68,[74][75][76].…”

Section: Resultsmentioning

confidence: 96%

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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Abstract:In the present work, an in-depth, qualitative and quantitative description of non-covalent interactions in the hydrogen storage materials LiN(CH 3 ) 2 BH 3 and KN(CH 3 ) 2 BH 3 was performed by means of the charge and energy decomposition method (ETS-NOCV) as well as the Interacting Quantum Atoms (IQA) approach. It was determined that both crystals are stabilized by electrostatically dominated intra-and intermolecular M¨¨¨H-B interactions (M = Li, K). For LiN(CH 3 ) 2 BH 3 the intramolecular charge transfer appeared (B-HÑLi) to be more pronounced compared with the corresponding intermolecular contribution. We clarified for the first time, based on the ETS-NOCV and IQA methods, that homopolar BH¨¨¨HB interactions in LiN(CH 3 ) 2 BH 3 can be considered as destabilizing (due to the dominance of repulsion caused by negatively charged borane units), despite the fact that some charge delocalization within BH¨¨¨HB contacts is enforced (which explains H¨¨¨H bond critical points found from the QTAIM method). Interestingly, quite similar (to BH¨¨¨HB) intermolecular homopolar dihydrogen bonds CH¨¨¨HC appared to significantly stabilize both crystals-the ETS-NOCV scheme allowed us to conclude that CH¨¨¨HC interactions are dispersion dominated, however, the electrostatic and σ/σ*(C-H) charge transfer contributions are also important. These interactions appeared to be more pronounced in KN(CH 3 ) 2 BH 3 compared with LiN(CH 3 ) 2 BH 3 .

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Section: Resultsmentioning

confidence: 96%

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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“…One has to decrease T to 100 K to observe 2, 9,11,15,19, and most of the heterodimers. By calculating Essential for pnicogen bonding is a charge transfer from D-to A-monomer in the sense of a through-space anomeric effect, which in the case of complexes such as 8 and 9 is better described as through-space second-order hyperconjugation or through-space skewed π-conjugation (see Figure 2).…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Strength of the Pnicogen Bond in Complexes Involving Group Va Elements N, P, and As

2014

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A set of 36 pnicogen homo- and heterodimers, R3E···ER3 and R3E···E′R′3, involving differently substituted group Va elements E = N, P, and As has been investigated at the ωB97X-D/aug-cc-pVTZ level of theory to determine the strength of the pnicogen bond with the help of the local E···E′ stretching force constants k(a). The latter are directly related to the amount of charge transferred from an E donor lone pair orbital to an E′ acceptor σ* orbital, in the sense of a through-space anomeric effect. This leads to a buildup of electron density in the intermonomer region and a distinct pnicogen bond strength order quantitatively assessed via k(a). However, the complex binding energy ΔE depends only partly on the pnicogen bond strength as H,E-attractions, H-bonding, dipole-dipole, or multipole-multipole attractions also contribute to the stability of pnicogen bonded dimers. A variation from through-space anomeric to second order hyperonjugative, and skewed π,π interactions is observed. Charge transfer into a π* substituent orbital of the acceptor increases the absolute value of ΔE by electrostatic effects but has a smaller impact on the pnicogen bond strength. A set of 10 dimers obtains its stability from covalent pnicogen bonding whereas all other dimers are stabilized by electrostatic interactions. The latter are quantified by the magnitude of the local intermonomer bending force constants XE···E′. Analysis of the frontier orbitals of monomer and dimer in connection with the investigation of electron difference densities, and atomic charges lead to a simple rationalization of the various facets of pnicogen bonding. The temperature at which a given dimer is observable under experimental conditions is provided.

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“…Perhaps the most readily accessible description for the origins of the X-bond is the σ-hole model 25 , which treats the interaction as primarily electrostatic (Figure 1b) 22 , although there remains significant controversy over the contribution of dispersion 26 and even charge-transfer 27 to the interaction. The model describes X-bonding as a consequence of a halogen forming a σ-bond, such as a C—X bond.…”

Section: Introductionmentioning

confidence: 99%

Force Field Model of Periodic Trends in Biomolecular Halogen Bonds

et al. 2014

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The study of the noncovalent interaction now defined as a halogen bond (X-bond) has become one of the fastest growing areas in experimental and theoretical chemistry—its applications as a design tool are highly extensive. The significance of the interaction in biology has only recently been recognized, but has now become important in medicinal chemistry. We had previously derived a set of empirical potential energy functions to model the structure-energy relationships for bromines in biomolecular X-bonds (BXBs). Here, we have extended this force field for BXBs (ffBXB) to the halogens (Cl, Br, and I) that are commonly seen to form stable X-bonds. The ffBXB calculated energies show a remarkable one-to-one linear relationship to explicit BXB energies determined from an experimental DNA junction system, thereby validating the approach and the model. The resulting parameters allow us to interpret the stabilizing effects of BXBs in terms of well-defined physical properties of the halogen atoms, including their size, shape, and charge, showing periodic trends that are predictable along the Group VII column of elements. Consequently, we have established the ffBXB as accurate computational tool that can be applied to, for example, for the design of new therapeutic compounds against clinically important targets and new biomolecular based materials.

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On The Nature of the Halogen Bond

Cited by 250 publications

References 79 publications

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

Strength of the Pnicogen Bond in Complexes Involving Group Va Elements N, P, and As

Force Field Model of Periodic Trends in Biomolecular Halogen Bonds

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