Cooperativity between fluorine-centered halogen bonds: investigation of substituent effects

Esraili, Mehdi D.; Mohammadian-Sabet, Fariba; Esmailpour, Parvin; Solimannejad, Mohammad

doi:10.1007/s00894-013-2032-4

Cited by 7 publications

(2 citation statements)

References 49 publications

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“…The tendency to form halogen bonds with Lewis bases increases as X goes down in the periodic table group. The fluorine atom in general is unable to form halogen-bonded complexes, although it could be achieved under certain conditions. − Among the more recurrent Lewis bases as halogen acceptors are found compounds containing O, N, halogens and S atoms. − Singlet carbenes have not attracted too much attention as Lewis bases.…”

Section: Introductionmentioning

confidence: 99%

Traditional and Ion-Pair Halogen-Bonded Complexes Between Chlorine and Bromine Derivatives and a Nitrogen-Heterocyclic Carbene

et al. 2014

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A theoretical study of the halogen-bonded complexes (A-X···C) formed between halogenated derivatives (A-X; A = F, Cl, Br, CN, CCH, CF3, CH3, H; and X = Cl, Br) and a nitrogen heterocyclic carbene, 1,3-dimethylimidazole-2-ylidene (MeIC) has been performed using MP2/aug'-cc-pVDZ level of theory. Two types of A-X:MeIC complexes, called here type-I and -II, were found and characterized. The first group is described by long C-X distances and small binding energies (8-54 kJ·mol(-1)). In general, these complexes show the traditional behavior of systems containing halogen-bonding interactions. The second type is characterized by short C-X distances and large binding energies (148-200 kJ·mol(-1)), and on the basis of the topological analysis of the electron density, they correspond to ion-pair halogen-bonded complexes. These complexes can be seen as the interaction between two charged fragments: A(-) and (+)[X-CIMe] with a high electrostatic contribution in the binding energy. The charge transfer between lone pair A(LP) to the σ* orbital of C-X bond is also identified as a significant stabilizing interaction in type-II complexes.

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Section: Introductionmentioning

confidence: 99%

Traditional and Ion-Pair Halogen-Bonded Complexes Between Chlorine and Bromine Derivatives and a Nitrogen-Heterocyclic Carbene

et al. 2014

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“…In complex systems with the presence of two or more non-covalent interactions, there is a mutual interplay between them, irrespective of whether they are of the same type [36,37] or different [38][39][40]. This mutual influence can lead to interesting cooperativity or synergic effects.…”

Section: Introductionmentioning

confidence: 97%

Effect of cation–π interaction on lithium and halogen bonds: a comparative study

Esrafili

Mohammadirad

2014

Molecular Physics

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Ab initio calculations have been performed to study the complex of M + -PhX-NCY (M = Li, Na; X = Li, Br and Y = H, OH and NH 2 ). The aim is to compare the mutual cooperative effects between cation-π and lithium/halogen interactions. These effects are studied in terms of geometric and energetic properties, 15 N chemical shielding parameters, molecular electrostatic potentials and natural bond orbital analyses. A positive cooperativity is observed on introduction of a cation-π interaction to the PhLi-NCY and PhBr-NCY dyads. The cation-π interaction has an enhancing effect on the halogen bond interaction energy, making it increased by152%-233%, whereas that of lithium bond interaction by 18%-22%. The enhancing mechanism is analysed in views with the atomic charges, charge transfer and electrostatic potentials.

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Substituent effects on cooperativity of pnicogen bonds

2014

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Substituent effects on cooperativity of P···N pnicogen bonds are studied in XH2P···NCH(2)P···NCY (X=F, Cl; Y=H, F, CN, OH, NH(2)) complexes using high-level ab initio calculations. An increased attraction or a positive cooperativity is observed on introduction of a third molecule to the XH(2)P···NCH(2)P and NCH(2)P···NCY dyads. The shortening of the each pnicogen bond distance in the triads is dependent on the strength of the P···N bond and is increased in the order Y = NH(2) > OH > H > F > CN. The energy decomposition analysis indicates that the polarization energy is the important element in the interaction energy of P···N bond and may be regarded as being responsible for the stabilization in these systems. Natural bond orbital theory is used to characterize the interactions and analyze their enhancement with varying orbital interactions.

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Cooperativity between fluorine-centered halogen bonds: investigation of substituent effects

Cited by 7 publications

References 49 publications

Traditional and Ion-Pair Halogen-Bonded Complexes Between Chlorine and Bromine Derivatives and a Nitrogen-Heterocyclic Carbene

Traditional and Ion-Pair Halogen-Bonded Complexes Between Chlorine and Bromine Derivatives and a Nitrogen-Heterocyclic Carbene

Effect of cation–π interaction on lithium and halogen bonds: a comparative study

Substituent effects on cooperativity of pnicogen bonds

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