Comparison of σ-Hole and π-Hole Tetrel Bonds Formed by Pyrazine and 1,4-Dicyanobenzene: The Interplay between Anion-π and Tetrel Bonds

Xu, Huili; Cheng, Jianbo; Yang, Xin; Liu, Zhenbo; Li, Wenzuo

doi:10.1002/cphc.201700660

Cited by 39 publications

(154 citation statements)

References 95 publications

(154 reference statements)

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“…As study of these noncovalent bonds progressed it soon became apparent that σ-holes are not the only regions of positive potential that may be present. In cases where the bridging atom lies in a planar (or nearly planar) bonding environment, a positive area can develop above this molecular plane [ 33 ]. Like σ-holes, these π-holes serve as sites of attraction for an approaching nucleophile [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

2018

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The σ-hole tetrel bonds formed by a tetravalent molecule are compared with those involving a π-hole above the tetrel atom in a trivalent bonding situation. The former are modeled by TH4, TH3F, and TH2F2 (T = Si, Ge, Sn) and the latter by TH2=CH2, THF=CH2, and TF2=CH2, all paired with NH3 as Lewis base. The latter π-bonded complexes are considerably more strongly bound, despite the near equivalence of the σ and π-hole intensities. The larger binding energies of the π-dimers are attributed to greater electrostatic attraction and orbital interaction. Each progressive replacement of H by F increases the strength of the tetrel bond, whether σ or π. The magnitudes of the maxima of the molecular electrostatic potential in the two types of systems are not good indicators of either the interaction energy or even the full Coulombic energy. The geometry of the Lewis acid is significantly distorted by the formation of the dimer, more so in the case of the σ-bonded complexes, and this deformation intensifies the σ and π holes.

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Section: Introductionmentioning

confidence: 99%

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

2018

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“…The interaction energy decomposition profile of these complex fits into the overall picture of a wide variety of noncovalent interactions in the literature, even for other decomposition schemes, e.g. SAPT or EDA [71,[95][96][97][103][104][105][106][107].…”

Section: Components Of Total Interaction Energymentioning

confidence: 76%

Interactions of (MY)6 (M = Zn, Cd; Y = O, S, Se) quantum dots with N-bases

2019

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Se, form double-layer drum-like structures containing MY covalent bonds. The positive regions near the M atoms attract the N atom of both NH 3 and NMe 3 so as to form a noncovalent M•••N bond. This bond is quite strong, with interaction energies exceeding 35 kcal/mol. The bond strength diminishes with reduced electronegativity of the Y atom (O > S > Se) and is stronger for M = Zn than for Cd. Trimethylation of the base enhances the bond strength. The interaction is dominated by the electrostatic component which accounts for some 60-70% of the total attractive force. The interaction increases the highest occupied molecular orbital-lowest unoccupied molecular orbital gap by between 0.1 and 0.2 eV.

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“…Interest in tetrel bonding has been steadily growing over the last few years, especially since the tetrahedral configuration of the sp 3 hybridized carbon atom is central to a significant portion of organic chemistry. Insights gained from studies of tetrel bonding may find potentially useful applications in fields such as organic synthesis and supramolecular chemistry; for example, tetrel bonding appears to be relevant for the well-known S N 2 organic reaction [ 18 ], hydrophobic interactions [ 22 ], and in protein folding and ligand-acceptor interactions [ 19 , 23 , 24 ].…”

Section: Introductionmentioning

confidence: 99%

Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

McDowell

Wang

2020

Molecules

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The interactions in model ionic YTX3···Z (Y = NC, F, Cl, Br; X = F, Cl, Br, Z = F−, Cl−, Br−, Li+) dyads containing the tetrel atoms, T = C, Si, Ge, were studied using ab initio computational methods, including an energy decomposition analysis, which found that the YTX3 molecules were stabilized by both anions (via tetrel bonding) and cations (via polarization). For the tetrel-bonded dyads, both the electrostatic and polarization forces make comparable contributions to the binding in the C-containing dyads, whereas, electrostatic forces are by far the largest contributor to the binding in the Si- and Ge-containing analogues. Model metastable Li+···NCTCl3···F− (T = C, Si, Ge) triads were found to be lower in energy than the combined energy of the Li+ + NCTCl3 + F− fragments. The pair energies and cooperative energies for these highly polar triads were also computed and discussed.

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Comparison of σ-Hole and π-Hole Tetrel Bonds Formed by Pyrazine and 1,4-Dicyanobenzene: The Interplay between Anion-π and Tetrel Bonds

Cited by 39 publications

References 95 publications

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

Interactions of (MY)6 (M = Zn, Cd; Y = O, S, Se) quantum dots with N-bases

Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

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