Competition between halogen bond and hydrogen bond in complexes of superalkali Li₃S and halogenated acetylene XCCH (X = F, Cl, Br, and I)

Abstract

Complexes of superalkali Li3S and XCCH (X = F, Cl, Br, and I) have been studied with theoretical calculations at the MP2/aug‐cc‐pVTZ level. Three types of structures are found: (A) the X atom combines with the S atom through a halogen bond; (B) the X atom interacts with the π electron of Li3S by a π halogen bond; (C) the H atom combines with the S atom through a hydrogen bond. For A and B, a heavier halogen atom makes the interaction stronger, while for C, the change of interaction energy is not obvious, showing a small dependence on the nature of the X atom in HCCX. A is more stable than B and their difference in stability decreases as X varies from Cl to I. For the F and Cl complexes, A is weaker than C, however, the former is stronger than the latter in the Br and I complexes. The above three types of interactions have been analyzed by means of electron localization function, electron density difference, and energy decomposition, and the results show that they have similar nature and features with conventional interactions. © 2014 Wiley Periodicals, Inc.

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

“…[29,30] By combining interactions that do not compete for the same binding sites, it is, in principle, possible to avoid or at least minimize ''synthon cross-over'', [31] thereby producing architectures of considerable complexity. [34][35][36][37][38][39][40][41][42][43] This is not only because HBs and XBs are similar in strength and properties, but also they are widely applicable to biochemistry and drug design. [33] There are many studies on the competition between various interactions, especially the competition between hydrogen and halogen bonds.…”

“…[33] There are many studies on the competition between various interactions, especially the competition between hydrogen and halogen bonds. [34][35][36][37][38][39][40][41][42][43] This is not only because HBs and XBs are similar in strength and properties, but also they are widely applicable to biochemistry and drug design. Alkorta et al studied HBs and XBs formed between hypohalous acid and three nitrogen-containing bases .…”

Mg3F7: A superhalogen with potential for new nanomaterials design

“…These hypervalent structures were given the name “superhalogens” by Gutsev and Boldyrev who proposed their existence in the early 1980s and have introduced a simple MX k + 1 formula, where M is the main group or the transition metal atom, X is a halogen atom, and k is the maximal formal valence of the atom M . Up to now, a great number of theoretical and experimental studies have been performed to explore new superhalogen species and find ways to increase their application scope . The main aim of investigating novel superhalogen systems is to deliver reliable data and predictions considering the possible use of such compounds as electron acceptors (oxidizing agents).…”

Complicated synergistic effects between metal–π interaction and halogen bonding involving MCCX

“…Compared with V X,max (0.0347-0.0540 a.u.) in HCCX, 58 the metal substitution results in a decrease of V X,max , and even the value of V Cl,max in LiCCCl is close to zero due to the strong electron-donating ability of Li atom. As expected, the value of V X,max shows an increasing tendency for the heavier halogen atom (Table 1).…”