Prediction and characterization of halogen bonds involving formamidine and its derivatives

An, Xiulin; Jiang, Lixia; Li, Wenzuo; Cheng, Jianbo

doi:10.1016/j.saa.2014.11.064

Cited by 5 publications

(3 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This abnormal result is primarily attributed to the larger dispersion interaction. If a methylene H atom in NHCH 2 is replaced by an amino group, the sp 2 ‐hybridized N atom forms an XB with ClCCH, and its interaction energy amounts to −3.4 kcal/mol, [ 73 ] which is larger by ~2 kcal/mol than that in 4‐PyCl···NH 3 .…”

Section: Discussion and Summarymentioning

confidence: 99%

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Wang

Xiao

2020

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

Ab initio calculations are performed for binary complexes of TrR 3 ÁÁÁ4-PyX/4-OPyX and 4-PyX/4-OPyXÁÁÁN-base (Tr = B, Al; R = H, Cl, Br, I; X = Cl, Br, I; N-base = HCN, NHCH 2 , NH 3). The halogen bond (XB) is weak but becomes stronger in the HCN(sp) < NH 3 (sp 3) < NHCH 2 (sp 2) pattern. Nitrogen oxidation can enhance the XB a little. The triel bond (TrB) is very strong, with interaction energy ranging from −35 to −58 kcal/mol. The TrB is weaker for the heavier halogen atom in the AlR 3 complex, while no such dependence is found in the BR 3 complex. The oxygen atom of 4-OPyX engages in a weaker TrB than the nitrogen atom of 4-PyX, inconsistent with the negative molecular electrostatic potentials (MEPs) on both atoms. Both TrB and XB are strengthened in TrR 3 ÁÁÁ4-PyX/4-PyOXÁÁÁN-base. The binding distance of the stronger TrB is shortened to less than that of the weaker XB, which is in contrast to that in BF 3 ÁÁÁNCHÁÁÁNCH, where the stronger TrB has a larger shortening in the binding distance. The cooperativity is explained by MEP and charge transfer.

show abstract

Section: Discussion and Summarymentioning

confidence: 99%

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Wang

Xiao

2020

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…We defined Δ r (C–X, X = Cl or I) as the change in the C–X bond length of CCl 4 or CH 3 I before and after complexion. The previous research shows that Δ r (C–X) values are negative in the FA–ClCF 3 and FA–BrCF 3 complexes, while Δ r (C–X) values in FA–ICF 3 is positive . Molecules with strong electronegative halogen atoms, such as F or Cl, are predicted to be more likely to form blue-shifted halogen complexes, whilst molecules with the I atom tend to form red-shifted halogen complexes with lengthened C–I bonds.…”

Section: Results and Discussionmentioning

confidence: 93%

“…The previous research shows that Δr(C−X) values are negative in the FA−ClCF 3 and FA−BrCF 3 complexes, while Δr(C−X) values in FA−ICF 3 is positive. 70 Molecules with strong electronegative halogen atoms, such as F or Cl, are predicted to be more likely to form blue-shifted halogen complexes, whilst molecules with the I atom tend to form red-shifted halogen complexes with lengthened C−I bonds. It can be seen in Table 1 that values of Δr(C−Cl) are all negative except for that in the C−Cl a •••π bond, indicating that C−Cl bonds are generally shortened and blue-shifted, as observed in the CF 3 Cl and CCl 4 complexes in the previous studies.…”

Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

Halogen Bonding in the Complexes of CH₃I and CCl₄ with Oxygen-Containing Halogen-Bond Acceptors

2017

View full text Add to dashboard Cite

Methyl iodine (CHI) and carbon tetrachloride (CCl) are both important volatile precursors for atmospheric ozone destruction. CHI and CCl can act as halogen bond donors to form molecular complexes with atmospheric organic species, such as 2,5-dihydrofuran, tetrahydrofuran, and acetone. This study characterized the halogen bonds in the CHI and CCl complexes using matrix isolation infrared spectroscopy and density functional theory calculations. With the combination of vibrational frequencies in spectra and the calculated interaction energies, frequencies and atoms-in-molecules analyses, we confirmed the formation of halogen-bonded complexes. CHI as a halogen-bond donor is comparable or slightly weaker than CCl, and furans involving ether oxygens are better halogen acceptors than acetone. The results help to understand the possibilities of formation of atmospheric molecular complexes that may influence the atmospheric chemical activities and enhance the aerosol formation.

show abstract

Abnormal Tetrel Bonds between Formamidine and TH₃F: Substituent Effects

Cheng

et al. 2018

ChemistrySelect

Self Cite

View full text Add to dashboard Cite

Ab initio calculations have been performed for the complexes of formamidine (FA) with TH3F (T=C, Si, Ge, and Sn) as well as the complexes of FA derivatives including CH3, NH2, OH, OCH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CF3, and F with SiH3F. In general, each complex is stabilized by both a main tetrel bond and a secondary interaction. The stability of the complex increases in the order T=C < Ge < Si < Sn, inconsistent with the magnitude of the σ‐hole on the tetrel atom. The (Z)‐FA complex is more stable than the (E)‐FA analogue. The imino nitrogen atom of FA is a better tetrel acceptor than most nitrogenated bases; it shows a particularly strong affinity for SiH3F with an interaction energy of ∼60 kJ/mol. Four electron‐donating groups give rise to the opposite effect on the strength of the tetrel bond: a weakening effect for OH and OCH3 but an enhancement for CH3 and NH2; the largest interaction energy occurs in CH3‐(Z)‐FA‐SiH3F, amounting to a magnitude of 80 kJ/mol. Two electron‐withdrawing groups have a larger weakening effect than OH and OCH3. The effect of the larger alkyl group is dependent on the type of complex. The weak complexes of CH3F are driven by electrostatic and dispersion interactions, while the strong complexes of TH3F (T=Si, Ge, and Sn) are dominated by electrostatic and polarization interactions, as well as orbital interactions.

show abstract

Prediction and characterization of halogen bonds involving formamidine and its derivatives

Cited by 5 publications

References 68 publications

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Halogen Bonding in the Complexes of CH₃I and CCl₄ with Oxygen-Containing Halogen-Bond Acceptors

Abnormal Tetrel Bonds between Formamidine and TH₃F: Substituent Effects

Contact Info

Product

Resources

About

Prediction and characterization of halogen bonds involving formamidine and its derivatives

Cited by 5 publications

References 68 publications

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds

Halogen Bonding in the Complexes of CH3I and CCl4 with Oxygen-Containing Halogen-Bond Acceptors

Abnormal Tetrel Bonds between Formamidine and TH3F: Substituent Effects

Contact Info

Product

Resources

About

Halogen Bonding in the Complexes of CH₃I and CCl₄ with Oxygen-Containing Halogen-Bond Acceptors

Abnormal Tetrel Bonds between Formamidine and TH₃F: Substituent Effects