Superalkali Li3M (M=Cl, Br, I) as a Lewis base in halogen bonding: A heavier halogen is a stronger Lewis base than a lighter halogen

Tian, Wenkai; Miao, Qian; Li, Wen-zuo; Cheng, Jianbo

doi:10.1016/j.comptc.2013.03.002

Cited by 10 publications

(4 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Akiba summarized the general situation regarding the structures and bonding of hypervalent halogens [33]. Hypervalent halogens have also been extensively studied in theoretical research [34,35].…”

Section: Introductionmentioning

confidence: 99%

The Tetrel Bonds of Hypervalent Halogen Compounds

Niu,

McDowell,

2023

Molecules

Self Cite

View full text Add to dashboard Cite

The tetrel bond between PhXF2Y(TF3) (T = C and Si; X = Cl, Br, and I; Y = F and Cl) and the electron donor MCN (M = Li and Na) was investigated at the M06-2X/aug-cc-pVDZ level of theory. As the electronegativity of the halogen atom X increases, the strength of the tetrel bond also increases, but as the electronegativity of the halogen atom Y increases, the strength of the tetrel bond decreases. The magnitude of the interaction energy in most –CF3 complexes was found to be less than 10 kcal/mol, but to exceed 11 kcal/mol for PhClF2Cl(CF3)⋯NCNa. The tetrel bond is greatly enhanced when the –SiF3 group interacts with LiCN or NaCN, with the largest interaction energy approaching 100 kcal/mol and displaying a covalent Si⋯N interaction. Along with this enhancement, the Si⋯N distance was found to be less than the X–Si bond length, the –SiF3 group to be closer to the N atom, and in most –SiF3 systems, the X–Si–F angle to be less than 90°; the –SiF3 group therefore undergoes inversion and complete transfer in some systems.

show abstract

Section: Introductionmentioning

confidence: 99%

The Tetrel Bonds of Hypervalent Halogen Compounds

Niu,

McDowell,

2023

Molecules

Self Cite

View full text Add to dashboard Cite

show abstract

“…Thus, it is interesting to combine the superatoms and molecules through noncovalent interactions, which would be very important for the construction of novel materials. Superhalogen and superalkali are two important types of superatoms.…”

Section: Introductionmentioning

confidence: 99%

“…The superhalogen MX 3 (M = Be, Mg, Ca; X = F, Cl, Br) brings out the similar substituent effects, which is beyond our expectation. Superalkali Li 3 M (M = halogen), as a Lewis base, can form a halogen bond with dihalogen molecules, and the halogen bond becomes stronger in the order of M = F < Cl < Br, which is reverse to the electronegativity of conventional halogen. These abnormal results inspire us to combine more superatoms with small molecules through noncovalent interactions.…”

Section: Introductionmentioning

confidence: 99%

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

Tian

2014

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…Already a large number of publications concerning the halogen bonds between small molecules are available . Conversely, there is only a handful of systematic experimental or theoretical reports on the B···XY complexes based on the aromatic moieties . In this context, we can mention the theoretical study of Wang et al where ab initio calculations were performed on the complexes of pyridine with F 2 , Cl 2 , Br 2 , BrF, and BrCl .…”

Section: Introductionmentioning

confidence: 99%

Substitution effect on the intermolecular halogen and hydrogen bonds of the σ‐bonded fluorinated pyridine···XY/HX complexes (XY = F₂, Cl₂, ClF; HX = HF, HCl)

Sládek

Punyain

Ilčin

et al. 2014

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Optimal structures, electronic and thermodynamic properties of the title complexes are presented. The stability of the hydrogen bonded systems is enhanced by the increasing dipole moments whereas in the halogen bonded systems it is also affected by the atom size in the diatomics. The consecutive addition of fluorine atoms to the pyridine moiety results in the decrease of the interaction energy for both types of the investigated bonds. The substitution on the meta sites in pyridine leads to more stable complexes than the substitution in the ortho position.The role of substitution on electric polarization and electrostatic forces is estimated by the symmetry-adapted perturbation theory energy decomposition. The predicted Gibbs free energies of the complexes of mono fluorinated pyridines with HCl, HF, and ClF are from 212 to 222 kJ mol 21 at 200 K. The possible experimental identification of the complexes with respect to the vibrational modes is discussed.

show abstract

Superalkali Li3M (M=Cl, Br, I) as a Lewis base in halogen bonding: A heavier halogen is a stronger Lewis base than a lighter halogen

Cited by 10 publications

References 48 publications

The Tetrel Bonds of Hypervalent Halogen Compounds

The Tetrel Bonds of Hypervalent Halogen Compounds

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

Substitution effect on the intermolecular halogen and hydrogen bonds of the σ‐bonded fluorinated pyridine···XY/HX complexes (XY = F₂, Cl₂, ClF; HX = HF, HCl)

Contact Info

Product

Resources

About

Superalkali Li3M (M=Cl, Br, I) as a Lewis base in halogen bonding: A heavier halogen is a stronger Lewis base than a lighter halogen

Cited by 10 publications

References 48 publications

The Tetrel Bonds of Hypervalent Halogen Compounds

The Tetrel Bonds of Hypervalent Halogen Compounds

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

Substitution effect on the intermolecular halogen and hydrogen bonds of the σ‐bonded fluorinated pyridine···XY/HX complexes (XY = F2, Cl2, ClF; HX = HF, HCl)

Contact Info

Product

Resources

About

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

Substitution effect on the intermolecular halogen and hydrogen bonds of the σ‐bonded fluorinated pyridine···XY/HX complexes (XY = F₂, Cl₂, ClF; HX = HF, HCl)