Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X=C and Si) and HCN

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

“…The MEP maps of TH 3 Fa nd F 2 TO have been reported previously. [27,52] Four s holes and two p holes were found on the tetrel atom in TH 3 Fa nd F 2 TO, respectively.T he largest s hole in TH 3 F is at the FÀTb ond end and its positive MEP value is smaller than that of the p hole on the correspondingt etrel atom of F 2 TO. Figure 1s hows the MEP maps of pyrazine (1)a nd 1,4-dicyanobenzene (2).…”

“…The p-hole tetrel bond has been studied in complexes of F 2 TX (T = C, Si, Ge, Sn;X = O, S, Se). [34,[50][51][52] Anion-p and lone pair (Lp)-p interactions also belong to phole interactions. [53] Here, s-hole and p-hole interactions are purelyC oulombic in nature,w hich also encompasses polarization and dispersion.…”

“…However,i tw as also shown that the strength of tetrel bonding can be regulated by ac ooperativity effect with itself or other types of interactions, such as hydrogen bonds, halogen bonds, chalcogen bonds, pnicogen bonds, lithium bonds, beryllium bonds, and cation-p interactions. [27,34,52,[65][66][67][68][69][70][71][72][73][74][75][76][77][78][79] However, no study has been performed on the cooperativity effect between anion-p and tetrel bond interactions. Based on the abovementioned conclusiont hat cooperativity effects are present between different types of interactions, the question arises as to whether ac ooperativity effect can be found when anion-p and tetrel bond interactions coexistint he same complex.…”

Quantification of &sigma;&ndash;Holes and Their Use as a Descriptor for the Theoretical Calculation of p<em>K</em>a Values for Carboxylic Acids

“…Therefore, tetrel bonds belong to a broader kind of directional non-covalent electrostatic interactions like halogen [6][7][8], chalcogen [9,10], and pnicogen bonds [11]. A stretch of this label has been applied to hydrogen bonding, despite the absence of p electrons on hydrogen atoms and the high polarizability of their bonds [12,13].…”

Competitive Halide Binding by Halogen Versus Hydrogen Bonding: Bis‐triazole Pyridinium

“…This Coulombic attraction is supplemented by the transfer of charge from the neighboring molecule's lone electronp airs into the CÀX s*a ntibonding orbital under the rubric of polarization or induction energy.A dditional attraction arises by way of Londond ispersion forces. It is worthwhile to notet hat this bondingm echanism is not limited to halogen atoms, but has been observed for chalcogen, [13][14][15][16][17][18][19][20][21] pnicogen, [12,[22][23][24][25][26][27][28] and tetrel [29][30][31][32][33][34][35][36] atoms in the eponymous bonds.…”