Anionic tetrel bonds: An ab initio study

Esrafili, Mehdi D.; Asadollahi, Soheila; Mousavian, Parisasadat

doi:10.1016/j.cplett.2017.11.051

Cited by 31 publications

(29 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A wider range of anions, up to triatomic, was considered in tetrel bonds to TF 4 and TF 3 CN. [29] Fluoride engaged in the strongest bonds, up to 84 kcal/mol for T = Si. Pb in particular binds strongly to anions [7d] as for example Pb(CH 3 ) 3 CN with chloride, with an interaction energy of 32 kcal/mol.…”

Section: Discussionmentioning

confidence: 99%

Noncovalent Bonds between Tetrel Atoms

et al. 2020

View full text Add to dashboard Cite

The pairing of TFH3 with a TH2CH3− anion, where T represents tetrel atoms C, Si, Ge, Sn, Pb, results in a strong direct interaction between the two T atoms. The interaction energy is sensitive to the nature of the two T atoms but can be as large as 90 kcal/mol. The noncovalent bond strength rises quickly as the basic T atom of the anion becomes smaller, or as the Lewis acid T grows larger, although there is less sensitivity to the latter atom. The electrostatic component makes up some 55–70 % of the total attraction energy. This term is well accounted for by simple combination of the maximum and minimum values of the molecular electrostatic potential of the Lewis acid and base units, respectively. The complexation induces a rearrangement in the TFH3 molecule from tetrahedral to trigonal pyramidal. The associated deformation energy reduces the exothermicity of the complexation reaction. Electron density shift patterns reveal a density loss on the basic T atom, along with accompanying increases on the acidic T and its attached F atom.

show abstract

Section: Discussionmentioning

confidence: 99%

Noncovalent Bonds between Tetrel Atoms

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Despite any barriers to their formation, these tetrel bonds occur widely and are of great import in a number of chemical and biological processes. [35][36][37][38][39][40][41][42] The scale and effects of the geometric deformation of the TR 4 molecule required to accommodate a Lewis base have been assessed quantitatively. [9,10] Scores of tetrel bonds have been identified within protein structures, [11][12][13][14][15] and are implicated in the catalytic process of several enzymes.…”

Section: Introductionmentioning

confidence: 99%

“…[31][32][33][34] This strengthening is amplified when either molecule acquires an electric charge. [35][36][37][38][39][40][41][42] The scale and effects of the geometric deformation of the TR 4 molecule required to accommodate a Lewis base have been assessed quantitatively. [43][44][45][46] There has also been some consideration of the rather unusual bases carbenes [47,48] or π-systems [33] as tetrel bond acceptors.…”

Section: Introductionmentioning

confidence: 99%

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

et al. 2019

View full text Add to dashboard Cite

In order to accommodate the approach of two NCH bases, a tetrahedral TF 4 molecule (T=Si, Ge, Sn, Pb) distorts into an octahedral structure in which the two bases can be situated either cis or trans to one another. The square planar geometry of TF 4 , associated with the trans arrangement of the bases, is higher in energy than its see-saw structure that corresponds to the cis trimer. On the other hand, the square geometry offers an unobstructed path of the bases to the π-holes above and below the tetrel atom and hence enjoys a higher interaction energy than is the case for the σ-holes approached by the bases in the cis arrangement. When these two effects are combined, the total binding energies are more exothermic for the cis than for the trans complexes. This preference amounts to some 3 kcal mol À 1 for Sn and Pb, but is amplified for the smaller tetrel atoms.[a] M. Michalczyk, Dr.

show abstract

“…A particular focus of the present study is tetrel-bonded clusters where the positive sigma–hole arising from the tetrel atom binds a model anion. Studies involving interactions between the sigma–hole regions of tetrel atoms and various anions, including halide anions, have been documented before in the literature [ 18 , 27 , 36 , 37 , 38 , 39 , 40 , 41 ]. A previous study of model ionic dyads X···AH 3 -Y (X = F − , Cl − , Br − , Li + and Be 2+ ; A = C, Si, Ge; Y = F, Cl, Br) reported on stable anionic and cationic dyads, with the strength of the interaction increasing as a function of the electric field of the ion [ 42 ].…”

Section: Introductionmentioning

confidence: 99%

Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

McDowell

Wang

2020

Molecules

View full text Add to dashboard Cite

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.

show abstract

Anionic tetrel bonds: An ab initio study

Cited by 31 publications

References 71 publications

Noncovalent Bonds between Tetrel Atoms

Noncovalent Bonds between Tetrel Atoms

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

Contact Info

Product

Resources

About

Anionic tetrel bonds: An ab initio study

Cited by 31 publications

References 71 publications

Noncovalent Bonds between Tetrel Atoms

Noncovalent Bonds between Tetrel Atoms

Hexacoordinated Tetrel‐Bonded Complexes between TF4 (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

Contact Info

Product

Resources

About

Hexacoordinated Tetrel‐Bonded Complexes between TF₄ (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes