Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO2

Abstract

The complexes formed by H 2 CO, CH 3 CHO, and (CH 3) 2 CO with 1, 2, and 3 molecules of CO 2 are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO 2 , and some supplemented by a CH••O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C= =O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding orbital. Heterotrimers and tetramers carry over many of the geometrical and bonding features of the binary complexes, but also introduce O••O chalcogen bonds. These larger complexes exhibit only small amounts of cooperativity.

An ab initio investigation of chalcogen–hydride interactions involving HXeH as a chalcogen bond acceptor

“…As Table 2 indicates, electrostatic interaction is identified as the major contributing factors for the stability of XCYÁÁÁHXeH complexes. These results are consistent with those of conventional chalcogen bonds [22][23][24][25]. The second most important attraction term in these complexes is dispersion (E disp ) term, which contributes to 22 % of all the attractive terms in the strongest complex, OCTeÁÁÁHXeH, and increases its contribution, reaching 43 % in the weakest complex, SCSÁÁÁHXeH.…”

“…The r-hole potential becomes stronger as the chalcogen atom Y becomes more polarizable (O\S\Se\Te) and as R becomes more electronwithdrawing relative to Y. The strengths of chalcogen bonds with a given negative site usually correlate with the magnitudes of the positive electrostatic potential associated with the r-holes [22][23][24][25], although the overall interaction energies may be considerably influenced by secondary interactions involving other portions of the molecules.…”

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

“…[58][59][60][61][62][63] To ensure the structures obtained were minima on the potential energy surface, frequency calculations were also performed at the same level, affirming all structures have no imaginary frequencies. [58][59][60][61][62][63] To ensure the structures obtained were minima on the potential energy surface, frequency calculations were also performed at the same level, affirming all structures have no imaginary frequencies.…”

Surface‐enhanced Raman scattering properties of Lewis acid–base complexes ofp‐hydroxybenzoic andp‐mercaptobenzoic acids with CO2in the presence of silver

“…Hence, by comparing SERS spectra, obtained under normal and scCO 2 conditions, possible effects from the intermolecular interactions could be further understood. In the case of PHBA and PMBA, the presence of an available carboxylic group would be sufficient to interact with a CO 2 molecule, giving rise to the so‐called Lewis acid–base (LA–LB) interactions . In this sense, we propose that SERS/scCO 2 spectroscopy can be also employed to rationalize LA–LB complexations involving noble metals.…”

“…In general, for many CO 2 ‐philic compounds, an LA–LB interaction may be accompanied by a weaker, although cooperative, C–H⋅⋅⋅O–H bonding . This latter interaction acts as an additional stabilizing source during the solvation process of CO 2 philes, with hydrogen atoms attached to an α ‐carbon of the solute . Thus, to quantify the effects of LA–LB interactions in PHBA and PMBA in scCO 2 , commonly used as adsorbed molecules on assembled nanoparticles, it is necessary to determine their structural, electronic, and spectral changes upon the interaction with CO 2 .…”