F or O, Which One Is the Better Hydrogen Bond (Is It?) Acceptor in C–H···X–C (X– = F–, O═) Interactions?

Saha, Binoy K.; Saha, Arijit; Sharada, Durgam; Rather, Sumair A.

doi:10.1021/acs.cgd.7b01164

Cited by 21 publications

(21 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that F atoms from the substrates maintain a long distance with the Al center, but a relatively short distance with methyl H atoms. All these suggest that interactions between NacNacAl (1) and substrates are dominated by C–H···F-type H-bond interactions (Saha et al, 2018). For substrate 4 , two binding conformations ( IM 1−4 and IM 1−4iso ) are located in calculation, which would lead to two distinct products as observed in experiments (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Zhang

Wang

et al. 2019

Front. Chem.

View full text Add to dashboard Cite

The oxidative addition of a range of robust aryl C–F bonds to a single Al(I) center supported by a (NacNac)− bidentate ligand ((NacNac)− = [ArNC(Me)CHC(Me)NAr]− and Ar = 2,6–Pr2iC6H3) have been explored by density functional theory calculations. Our calculations demonstrate that the Al(I) center-mediated C–F insertion generally proceeds via the concerted mechanism that involve both the donation (nAl→σC-F*) and back-donation (σF(p)→πAl(p)*) interactions. In addition, the predicted free energy barriers for the C–F bond activation show good agreement with the experimental information available. Finally, the comparative studies show that B(I) is the most active among group III metals (B, Al, Ga), thus supplying a testable prediction for experiments.

show abstract

Section: Resultsmentioning

confidence: 99%

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Zhang

Wang

et al. 2019

Front. Chem.

View full text Add to dashboard Cite

show abstract

“…As discussed previously on several occasions, fluorine‐centered non‐covalent interactions can be weak and directional . This is likely to arise from a universal intermolecular dispersion, either reinforced or opposed by a Columbic force.…”

Section: Introductionmentioning

confidence: 81%

Revealing Factors Influencing the Fluorine‐Centered Non‐Covalent Interactions in Some Fluorine‐Substituted Molecular Complexes: Insights from First‐Principles Studies

2018

View full text Add to dashboard Cite

We examine the equilibrium structure and properties of six fully or partially fluorinated hydrocarbons and several of their binary complexes using computational methods. In the monomers, the electrostatic surface of the fluorine is predicted to be either entirely negative or weakly positive. However, its lateral sites are always negative. This enables the fluorine to display an anisotropic distribution of charge density on its electrostatic surface. While this is the electrostatic surface scenario of the fluorine atom, its negative sites in some of these monomers are shown to have the potential to engage in attractive engagements with the negative site(s) on the same atom in another molecule of the same type, or a molecule of a different type, to form bimolecular complexes. This is revealed by analyzing the results of current state-of-the-art computational approaches such as DFT, together with those obtained from the quantum theory of atoms in molecules, molecular electrostatic surface potential and symmetry adapted perturbation theories. We demonstrate that the intermolecular interaction energy arising in part from the universal London dispersion, which has been underappreciated for decades, is an essential factor in explaining the attraction between the negative sites, although energy arising from polarization strengthens the extent of the intermolecular interactions in these complexes.

show abstract

“…The competition between C-H/O and C-H/F-C has been the subject of heated discussions. 21,[47][48][49][50][51][52] To clarify this problem, we combined the Cambridge Structural Database (CSD) screening 53 with the results of periodic DFT computations of the crystals of partly uorinated molecules with C-H/O interactions.…”

Section: Introductionmentioning

confidence: 99%

Solving the enigma of weak fluorine contacts in the solid state: a periodic DFT study of fluorinated organic crystals

et al. 2019

View full text Add to dashboard Cite

show abstract

F or O, Which One Is the Better Hydrogen Bond (Is It?) Acceptor in C–H···X–C (X– = F–, O═) Interactions?

Abstract: The refcode list for the structures containing C, H, F, and O elements and some relevant tables (PDF)

Cited by 21 publications

References 33 publications

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Revealing Factors Influencing the Fluorine‐Centered Non‐Covalent Interactions in Some Fluorine‐Substituted Molecular Complexes: Insights from First‐Principles Studies

Solving the enigma of weak fluorine contacts in the solid state: a periodic DFT study of fluorinated organic crystals

Contact Info

Product

Resources

About