Bifurcated Hydrogen Bonds:  Three-Centered Interactions

Abstract

The nature of bifurcated or three-centered hydrogen bonds (HB) has been investigated. Different families of compounds were chosen: monomers with intramolecular three-centered HB, dimers with a HB donor (HBD) and a molecule with two HB acceptor (HBA) groups, and trimers with one HBD and two HBAs. All the systems were optimized at the B3LYP/6-31G* level, and, in the case of the complexes, the interaction energies were evaluated and corrected with the basis set superposition error (BSSE). The electronic nature of these three-centered HBs was analyzed by means of the atoms in molecules (AIM) approach. The present study indicates the existence of bifurcated bond paths in the AIM analysis with electron densities that can be classified as follows: (i) compounds with symmetric three-centered HBs presenting two symmetric bond critical points with equal values of electron density; (ii) compounds with asymmetric three-centered HBs presenting two bond critical points with different values of electron density; (iii) compounds with a regular HB and a van der Waals interaction showing two bond critical points with different electron density values one of which is very small; (iv) van der Waals complexes with two bond critical points having very small electron densities. Therefore, looking at the geometry, electron density, and energy results, the nature as HB of these three-centered interactions has been confirmed.

Review on DFT and ab initio Calculations of Scalar Coupling Constants

“…For instance, other interactions deserved to be explored like inverse HBs [51,52], three-centered (bifurcated) HBs [53], charge-transfer bonds [54], etc. One of the main objectives that should be approached in the next years is the calculation of coupling constants including heavy atoms (therefore, including relativistic corrections) because the structure of many fundamental problems in chemistry (catalysis) and biochemistry involve these atoms.…”

Matrix Metalloproteinase-10 (MMP-10) Interaction with Tissue Inhibitors of Metalloproteinases TIMP-1 and TIMP-2

“…Accordingly, we examined the stromelysin/TIMP-1 interfaces to identify differences in polar contacts. Enumerating the interfacial salt bridges and hydrogen bonds in the two complexes (Table 3), we observed that the MMP-10cd⅐TIMP-1 structure has three salt bridges, one of which fulfills H-bonding criteria, and 18 additional H-bonds, including one bifurcated three-center H-bond (65,66). In comparison, the MMP-3cd⅐TIMP-1 structure also possesses three salt bridges, two of which fulfill H-bonding criteria, and 21 additional H-bonds, three more than in the MMP10cd⅐TIMP-1 structure.…”

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

“…These studies support the notion that intermolecular bifurcated H-bond formation is a process that gives rise to negative cooperative effects. 36,37 For intramolecular bifurcated H bonds, examples of positive and negative cooperative effects have been reported. [38][39][40] The importance of resonance-assisted hydrogen bonding ͑RAHB͒ in bifurcated hydrogen bonds was recently pointed out by Rybarczyk-Pirek et al 41 for the crystal structures of some new phosphorochromone derivatives.…”