Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

San‐Fabián, Emilio; Ingrosso, Francesca; Lambert, Alexandrine; Bernal-Uruchurtu, Margarita I.; Ruiz‐López, Manuel F.

doi:10.1016/j.cplett.2014.03.084

Cited by 16 publications

(13 citation statements)

References 35 publications

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“…8 This type of stabilising interaction was reported in different systems and the interaction is reminiscent of the Bürgi-Dunitz trajectory for nucleophilic additions to carbonyl groups and eventually should provoke pyramidalisation of the acceptor carbonyl group. [20][21][22][23] The conformation B obtained in water is almost identical to that found for acetonitrile (see Figure 6 and Figure 7). interaction (NCI) plots for conformation B in acetonitrile.…”

Section: Resultssupporting

confidence: 72%

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

Crowe¹,

Nicholson²,

Fleming³

et al. 2017

Bioorganic & Medicinal Chemistry

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In their 1 H NMR spectra in CDCl 3 3-oxo-N-acyl homoserine lactones (OHLs) show significant downfield chemical shifts of the amide N-H proton when compared to the parent N-acyl homoserine lactones (AHLs). NMR spectroscopic and DFT calculation studies have shown that this is most likely due to the presence of a stabilising intramolecular H-bond from the N-H to the 3-oxo group. The 1 H NMR spectra also show evidence for the enol tautomers and that the amount of enol present for a range of OHLs is 4.1-4.5% in CDCl 3 and 6.5-7.2% in CD 3 CN. In contrast, DFT calculations show that the lowest energy enol tautomer and the keto tautomer are of equal energy in the gas phase, but that the keto tautomer is more stable in chloroform, acetonitrile and water solution. The calculations also show that there is no evidence for any n→* or C5 H-bonding interactions being present in either the lowest energy keto or enol tautomer of the OHLs in solution or the gas phase, which is in contrast to the reported solid-state structure.

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Section: Resultssupporting

confidence: 72%

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

Crowe¹,

Nicholson²,

Fleming³

et al. 2017

Bioorganic & Medicinal Chemistry

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“…[5][6][7][8][9][10] CO 2 has also been the subject of numerous computational studies. [11][12][13][14][15][16] Other efforts have added to understanding the interactions of CO 2 with various solutes, especially those containing carbonyl functional groups or aromatic systems and other heteroatoms as nitrogen, sulfur, or halogens in their compositions. [17][18][19][20][21][22][23][24][25][26][27][28] These works have added to our understanding by providing a clear definition of the conformational landscape in systems in which CO 2 acts as both electron acceptor and donor in noncovalent complexes with different solutes and in the presence of a variety of heteroatoms in their compositions, which offer many peculiarities in their structures.…”

Section: Introductionmentioning

confidence: 99%

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

Azofra

Scheiner

2015

The Journal of Chemical Physics

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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.

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“…Both complexes are supposed to be mostly stabilized by the interaction between the carboxylic group oxygen atom and the electron‐deficient carbon atom of CO 2 . This assumption is noticed by the structural evidence of a C = O⋅⋅⋅C bond formed in both complexes, which exhibit a characteristic geometry of LA–LB complexation, similar to that occurring in other carbonyl compounds with CO 2 . The interaction with Ag is represented by substituting the hydrogen atom covalently bonded to the X atom (as indicated in Fig.…”

Section: Resultsmentioning

confidence: 65%

“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Filho

Cunha

Rivelino

2016

J Raman Spectroscopy

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Effects of local environment on the sensitivity of surface‐enhanced Raman scattering have been recently considered as an important issue in experiments involving charge‐transfer mechanism between the adsorbed molecules and the metal surface. To theoretically investigate this issue, we consider the complexation of p‐hydroxybenzoic acid (PHBA) and p‐mercaptobenzoic acid (PMBA) with carbon dioxide (CO2), and in contact with silver (Ag), by means of ab initio calculations. Within the Møller–Plesset perturbation theory, it is demonstrated that the carboxylic group of PHBA or PMBA can act as an electron‐donating site, binding the electron‐deficient carbon atom of CO2, via a Lewis acid–base (LA–LB) interaction. Changes in the vibrational spectra of these molecules are carefully determined and attributed to both LA–LB complexation with CO2 and interaction with Ag. Calculated Raman scattering shifts for the complexes also indicate that the chemical nature of the substituent group at para position of the aromatic ring can dramatically alter the signal of typical shifts expected for LA–LB complexes, as well as affect surface‐enhanced Raman scattering intensities. The LA–LB complexation is also reinforced by the ultraviolet–visible absorption spectra for the complexes, calculated within time‐dependent density functional theory and combined with the polarizable continuum model, employed to simulate the local environment dielectric constant. It is demonstrated that the lowest singlet π–π* excitation of both LA–LB complexes, PHBA and PMBA weakly bound to CO2, is significantly red shifted, which gives evidence for such a complexation. Copyright © 2016 John Wiley & Sons, Ltd.

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Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

Cited by 16 publications

References 35 publications

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

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

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

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Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

Cited by 16 publications

References 35 publications

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N -acyl homoserine lactone molecules

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

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

Contact Info

Product

Resources

About

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