“Pnicogen bonds” or “chalcogen bonds”: exploiting the effect of substitution on the formation of P⋯Se noncovalent bonds

Shukla, Rahul; Chopra, Deepak

doi:10.1039/c6cp01703g

Cited by 57 publications

(36 citation statements)

References 101 publications

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“…The highest percentage contribution of electrostatics and polarization combined with the lowest percentage contribution of dispersion towards the stability of NO4 can be attributed to the dual character of pnicogen and chalcogen bonds in the complex. In contrast to previously studied chalcogen and pnicogen bonds, 66,68,74 the contribution of the electrostatic energy was observed to be less than that of dispersion energy. This shows that the characteristics of NÁ Á ÁO contacts are quite different from the previously studied s-hole interactions.…”

Section: Resultscontrasting

confidence: 99%

Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

Shukla

Chopra

2016

Phys. Chem. Chem. Phys.

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In this article, the existence of NO noncovalent interactions was explored in per-halo substituted ammonia-water complexes. Optimized geometry at the MP2/aug-cc-pVTZ level shows that the NO distance in all complexes is less than the sum of the vdW radii of N and O. The strength of these contacts was directly dependent on the extent of chlorine substitution on N or O atoms. Also, the level of theory and the basis set employed for the binding energy calculations have a direct effect on the strength of the NO contacts. Energy decomposition analysis reveals that dispersion was the major contributor towards the stability of these contacts followed by electrostatic energy. The topological analysis further confirmed the existence of NO contacts due to the presence of a bond critical point between the N and the O atom in all the complexes. These contacts have characteristics of a σ-hole interaction with the NBO analysis revealing that the primary charge transfer in all the complexes is occurring from O(lp) to σ*(N-X) orbitals, confirming these interactions to be predominantly in the category of pnicogen bonds.

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Section: Resultscontrasting

confidence: 99%

Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

Shukla

Chopra

2016

Phys. Chem. Chem. Phys.

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“…The aug-cc-pVDZ-PP pseudopotential from the EMSL library [47][48] was used for Sn so as to account for relativistic effects. This level of theory has demonstrated its accuracy and effectiveness in numerous previous studies [49][50][51][52][53][54][55][56][57][58][59][60][61] of related systems.…”

Section: Systems and Methodsmentioning

confidence: 96%

Systematic Elucidation of Factors That Influence the Strength of Tetrel Bonds

2017

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Quantum calculations are used to examine the properties of heterodimers formed by a series of tetrel-containing molecules with NH as universal Lewis base. TH was taken as a starting point, with T = C, Si, Ge, and Sn. The H atoms were replaced by various numbers of F atoms-THF, TFH, and TF-so as to monitor the effects of adding electron-withdrawing substituents. Unsubstituted TH molecules form the weakest tetrel bonds, only up to about 2 kcal/mol. The bond is strengthened when the H opposite NH is replaced by F, rising up to the 6-9 kcal/mol range. Another means of strengthening arises when the three peripheral H atoms of TH are replaced by F. The effect of the latter is heavily dependent on the nature of the T atom and is particularly noticeable for larger tetrels. The two sorts of fluorination patterns are cooperative, in that their combination in TF yields by far the most powerful tetrel bonding agent. The tetrel bond is strengthened as the T atom moves further down the periodic table column. The strongest bond amounts to 25.5 kcal/mol for SnF··NH. A number of features correlate with the binding energy, but only roughly. These properties include the charge transfer, the AIM bond critical point electron density, the molecular electrostatic potential, and the stretch of the T-X covalent bond upon complex formation.

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“…Calculations were carried out within the context of Gaussian-09 69 , with the MP2 treatment of electron correlation, in concert with an aug-cc-pVDZ basis set. This level of theory has demonstrated its accuracy for Hbonds as well as other noncovalent bonds of the sort examined here 10,[70][71][72][73][74][75][76][77][78][79][80] . The presence of several methyl groups on the Lewis acid leads to strong coupling between the normal vibrational modes of the CH3 of interest and those of the others, which complicates any interpretation.…”

Section: Systems and Methodsmentioning

confidence: 99%

Ability of IR and NMR Spectral Data to Distinguish between a Tetrel Bond and a Hydrogen Bond

Scheiner

2018

J. Phys. Chem. A

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The placement of a nucleophile X along the R-CH axis of a methyl group can be described as either a trifurcated H bond or as a tetrel bond between C and X. Quantum calculations of the vibrational and NMR spectral features of a number of systems are used to provide a framework by which to distinguish between the presence of a tetrel or H bond. Both cationic and neutral methyl-containing Lewis acids (SMe, NMe, SMe) are paired with both neutral and anionic Lewis bases (NH, OH, OCHNH, OCH, OH, HCOO). As the base is moved away from the R-CH axis of the Lewis acid (tetrel bond) toward a position along a CH axis (CH···X H bond), the methyl stretching frequencies shift to the red, and the bending modes shift to the blue. This modification in the geometry also causes the methyl C atom NMR chemical shielding to increase, while the methyl H atom is progressively deshielded. These changes are of sufficiently large magnitude that they should provide a means to distinguish these two bonding situations from one another.

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“Pnicogen bonds” or “chalcogen bonds”: exploiting the effect of substitution on the formation of P⋯Se noncovalent bonds

Cited by 57 publications

References 101 publications

Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

Characterization of N⋯O non-covalent interactions involving σ-holes: “electrostatics” or “dispersion”

Systematic Elucidation of Factors That Influence the Strength of Tetrel Bonds

Ability of IR and NMR Spectral Data to Distinguish between a Tetrel Bond and a Hydrogen Bond

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