Comment on “Destabilization of the halogen bond in complexes of protonated NCX (X = F, Cl, Br) molecules” [Chem. Phys. Lett. 603 (2014) 37–40]

McDowell, Sean A. C.; Joseph, Jerelle A.; Buckingham, A. D.

doi:10.1016/j.cplett.2015.01.017

Cited by 1 publication

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“…for NCF). This unusual finding raised several intriguing questions relating to the bonding characteristics of such molecules, some of which were the motivation for a recent paper by the present authors [25].…”

Section: Introductionmentioning

confidence: 92%

“…However, polarisation by the cation also causes the lone pairs on the X atom to be pulled into a more confined space around the X nucleus. This contracting effect leads to increased repulsion between the X lone pairs and the O lone pairs, which ultimately destabilises the halogen bond, [25] and consequently no stable dimers are obtained.…”

Section: Neutral Complexesmentioning

confidence: 99%

“…[25] It was shown that for some cases the H + -NCX···Y complex was stronger than the corresponding NCX···Y complex, while in other instances the proton attachment apparently destabilised the halogen bond (due to increased inter-electronic repulsion). The study also indicated an apparent deficiency Table 1.…”

Section: Introductionmentioning

confidence: 98%

“…The properties include the interaction energy ( E in kJ mol −1 ), bond distances (R in Å ), harmonic vibrational frequency shifts ( ω in cm −1 ) and bond angles (in degrees). in the electrostatic approach (with regards to halogen bonding), suggesting that a strongly positive σ -hole on X may not be a sufficient condition for the formation of a halogen bond, given the existence of even stronger repulsive forces [25]. This work further explores the molecular surface of NCX, and specifically, the ability of a cationic electrophile (M = H + , Be 2 + ) to attach to the positive X surface to form stable NCX-M species.…”

Section: Introductionmentioning

confidence: 98%

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A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)

McDowell

Joseph

2014

Molecular Physics

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A MP2/6-311 ++ G(d,p) study of NCX (X = F, Cl, Br) has shown that it is possible to attach an electrophile (H + , Be 2 + ) to the positive halogen X surface of NCX. The stability and properties of model halogen-bonded and π -hole carbon-bonded NCX/H 2 O complexes were found to be significantly affected by H + or Be 2 + cationic attachment at the N atom. The halogen-bonded complexes are destabilised by binding at the N, while an attached proton enhances the binding in the π -hole bonded dimers. For the attached Be 2 + , an unusual complex was obtained with the NCF subunit, whereas the complexes containing Cl and Br were destabilised by the interaction. IntroductionNon-covalent interactions have commanded much interest in chemistry over the last few decades; one such interaction is the halogen bond. The halogen bond can be described as an attractive interaction between a covalently bonded group VII atom X (in a molecule R-X, where R is an electron-withdrawing atom or group) and an electron-rich site B (such as an anion or lone pair) [1-6]. Halogen bonds parallel hydrogen bonds in many respects [7] and have the potential for applications in several fields, such as crystal engineering and drug design [8][9][10][11].Though this type of interaction has been documented as far back as 1863 [12], it was only recently that its origins were interpreted [1,3]. Recall that the halogens are generally regarded as electronegative atoms, and as such are not expected to behave as electrophilic sites in their molecules. Halogen bonding is best understood by considering an anisotropic model for the electronic charge distribution of X, whereby charge is depleted in the region adjacent to the R-X σ -bond and charge is concentrated (i.e. the lone pairs) in a direction orthogonal to the R-X bond axis [1,2,13]. Consequently, X can act as an electron acceptor while retaining its characteristic nucleophilic property [14]. Additionally, because the electron-depleted regions on X are localised, R-X···B interactions tend to be highly directional -with a bond angle of about 180 • [15,16].The anisotropy of the halogen charge distribution in halogen bonds makes it difficult to model this type of interaction using an atomic point-charge assignment scheme, since this approach cannot account for the dual

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Section: Introductionmentioning

confidence: 92%

Section: Neutral Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 98%

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A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)

McDowell

Joseph

2014

Molecular Physics

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Comment on “Destabilization of the halogen bond in complexes of protonated NCX (X = F, Cl, Br) molecules” [Chem. Phys. Lett. 603 (2014) 37–40]

Cited by 1 publication

References 5 publications

A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)

A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)

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Comment on “Destabilization of the halogen bond in complexes of protonated NCX (X = F, Cl, Br) molecules” [Chem. Phys. Lett. 603 (2014) 37–40]

Cited by 1 publication

References 5 publications

A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H2O (X = F, Cl, Br)

A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H2O (X = F, Cl, Br)

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A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)

A comparative study of model halogen-bonded,π-hole-bonded and cationic complexes involving NCX AND H₂O (X = F, Cl, Br)