Interaction between amines and N-haloimides: a new motif for unprecedentedly short Br⋯N and I⋯N halogen bonds

Raatikainen, Kari

doi:10.1039/c1ce05447c

Cited by 98 publications

(98 citation statements)

References 40 publications

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“…Several types of halogen bonds, such as the halogen bond of nitro-iodo-benzenes, halopyridiniums and haloamides and imides, have been reported. [49][50][51] The structures of complexes formed by halogen bonds in the gas phase have been studied by microwave spectroscopy. [30][31][32] Halogen bonds in crystals have been studied by X-ray diffraction and by statistical analysis of the crystal structure database.…”

mentioning

confidence: 99%

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Tsuzuki

Wakisaka

Ono

et al. 2011

Chemistry A European J

123

118

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The geometries and interaction energies of complexes of pyridine with C6F5X, C6H5X (X=I, Br, Cl, F and H) and RFI (RF=CF3, C2F5 and C3F7) have been studied by ab initio molecular orbital calculations. The CCSD(T) interaction energies (Eint) for the C6F5X–pyridine (X=I, Br, Cl, F and H) complexes at the basis set limit were estimated to be −5.59, −4.06, −2.78, −0.19 and −4.37 kcal mol−1, respectively, whereas the Eint values for the C6H5X–pyridine (X=I, Br, Cl and H) complexes were estimated to be −3.27, −2.17, −1.23 and −1.78 kcal mol−1, respectively. Electrostatic interactions are the cause of the halogen dependence of the interaction energies and the enhancement of the attraction by the fluorine atoms in C6F5X. The values of Eint estimated for the RFI–pyridine (RF=CF3, C2F5 and C3F7) complexes (−5.14, −5.38 and −5.44 kcal mol−1, respectively) are close to that for the C6F5I–pyridine complex. Electrostatic interactions are the major source of the attraction in the strong halogen bond although induction and dispersion interactions also contribute to the attraction. Short‐range (charge‐transfer) interactions do not contribute significantly to the attraction. The magnitude of the directionality of the halogen bond correlates with the magnitude of the attraction. Electrostatic interactions are mainly responsible for the directionality of the halogen bond. The directionality of halogen bonds involving iodine and bromine is high, whereas that of chlorine is low and that of fluorine is negligible. The directionality of the halogen bonds in the C6F5I– and C2F5I–pyridine complexes is higher than that in the hydrogen bonds in the water dimer and water–formaldehyde complex. The calculations suggest that the CI and CBr halogen bonds play an important role in controlling the structures of molecular assemblies, that the CCl bonds play a less important role and that CF bonds have a negligible impact.

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confidence: 99%

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Tsuzuki

Wakisaka

Ono

et al. 2011

Chemistry A European J

123

118

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“…It is also interesting to see that, indeed, in the solid-state structure of HMTA/NBS only 1:2 adducts can be detected, whereas substituting NBS with N-iodosuccinimide (NIS), 1:4 adducts are clearly visible. [69] Unfortunately, the HMTA/NIS adduct was too insoluble to allow any PGSE measurement.…”

Section: Eq 10mentioning

confidence: 99%

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Ciancaleoni¹

2017

Preprint

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Abstract:In the last 20 years, a huge amount of experimental results about halogen bonding (XB) has been produced. Most of the systems have been characterized by solid state X-ray crystallography, whereas in solution the only routine technique is the titration (by using 1 H and 19 F NMR, IR, UV-Vis or Raman spectroscopies, depending on the nature of the system), with the aim of characterizing the strength of the XB interaction. Unfortunately, the titration techniques have many intrinsic limitations and they should be coupled with other, more sophisticated techniques to have an accurate and detailed description of the geometry and stoichiometry of the XB adduct in solution. In this review, it will be shown how crucial information about XB adducts can be obtained by advanced NMR techniques, as Nuclear Overhauser Effect-based Spectroscopies (NOESY, ROESY, HOESY…) and diffusion NMR techniques (PGSE or DOSY).

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“…It is also interesting to see that, indeed, in the solid-state structure of HMTA/NBS only 1:2 adducts can be detected, whereas substituting NBS with N-iodosuccinimide (NIS), 1:4 adducts are clearly visible [114]. Unfortunately, the HMTA/NIS adduct was too insoluble to allow any PGSE measurement.…”

Section: Diffusion Nmrmentioning

confidence: 99%

“…The authors used the theoretical charge displacement function analysis method [110][111][112][113] to demonstrate the anti-cooperative nature of XB interactions in this system: when one nitrogen donates electronic density to a NBS moiety, the other nitrogens become less basic and, therefore, less able to establish a new XB. It is also interesting to see that, indeed, in the solid-state structure of HMTA/NBS only 1:2 adducts can be detected, whereas substituting NBS with N-iodosuccinimide (NIS), 1:4 adducts are clearly visible [114]. Unfortunately, the HMTA/NIS adduct was too insoluble to allow any PGSE measurement.…”

Section: Diffusion Nmrmentioning

confidence: 99%

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Ciancaleoni

2017

Magnetochemistry

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Abstract:In the last 20 years, a huge volume of experimental work into halogen bonding (XB) has been produced. Most of the systems have been characterized by solid state X-ray crystallography, whereas in solution the only routine technique is titration (by using 1 H and 19 F nuclear magnetic resonance (NMR), infrared (IR), ultraviolet-visible (UV-Vis) or Raman spectroscopies, depending on the nature of the system), with the aim of characterizing the strength of the XB interaction. Unfortunately, titration techniques have many intrinsic limitations and they should be coupled with other, more sophisticated techniques to provide an accurate and detailed description of the geometry and stoichiometry of the XB adduct in solution. This review will show how crucial information about XB adducts can be obtained by advanced NMR techniques, nuclear Overhauser effect-based spectroscopies (NOESY, ROESY, HOESY . . . ) and diffusion NMR techniques (PGSE or DOSY).

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Interaction between amines and N-haloimides: a new motif for unprecedentedly short Br⋯N and I⋯N halogen bonds

Cited by 98 publications

References 40 publications

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

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Interaction between amines and N-haloimides: a new motif for unprecedentedly short Br⋯N and I⋯N halogen bonds

Cited by 98 publications

References 40 publications

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C6F5X and C6H5X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C6F5X and C6H5X (X=I, Br, Cl and F) with Pyridine

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Contact Info

Product

Resources

About

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine