Symmetry of hydrogen bonds in solution

Perrin, Charles L.

doi:10.1351/pac-con-08-08-14

Cited by 62 publications

(86 citation statements)

References 122 publications

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“…This includes monographs [1,2,3,4,5,6,7,8,9], as well as critical reviews [10,11,12,13,14,15,16,17,18,19,20,21]. The specificity of isotope effects in hydrogen bonded systems comes into prominence particularly due to an anharmonicity of the potential for the hydrogen/deuteron motion as well as due to the tunneling effect.…”

Section: Introductionmentioning

confidence: 99%

H/D Isotope Effects in Hydrogen Bonded Systems

2013

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An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio νH/νD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δδ (1H,2H) on δ (1H). This effect corresponds to the range of maximum on the correlation curve between δH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

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Section: Introductionmentioning

confidence: 99%

H/D Isotope Effects in Hydrogen Bonded Systems

2013

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“…By extension, these studies have been interpreted as denying any extra stabilization associated with short-strong hydrogen bonds. 19 …”

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confidence: 99%

Isotope-Induced Desymmetrization Can Mimic Isotopic Perturbation of Equilibria. On the Symmetry of Bromonium Ions and Hydrogen Bonds

Bogle

Singleton

2011

J. Am. Chem. Soc.

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The desymmetrizing effect of isotopic substitution on the geometry of otherwise symmetrical structures can be surprisingly large when there is anharmonic coupling between a desymmetrizing mode and modes whose zero-point energies are strongly isotope-dependent. This phenomenon is found to account for experimental observations that had been previously interpreted as implying asymmetry in bromonium ions and in hydrogen phthalate ions in aprotic solvents. The unlabeled structures are concluded to have the higher symmetry found in computed structures. Great care must be taken in applying isotopic perturbation as a test of asymmetry.

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“…In contrast, a symmetric structure presupposes two equally long and strong NÁ Á ÁX halogen bonds, none of them being fully primary or secondary yet both possessing some covalent character while also retaining features typical for secondary interactions. Analogous three-center hydrogen bonds were frequently claimed to prefer the symmetric arrangement in solution and to be unusually strong; however, decades of investigations were unable to provide evidence for this hypothesis [78,79]. Recent solution NMR studies addressed the nature of the [N-I-N] + and [N-Br- Fig.…”

Section: Charged Three-center Halogen Bond Complexesmentioning

confidence: 99%

Halogen Bonding in Solution

Carlsson

Veiga

Erdélyi

2014

Topics in Current Chemistry

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Because of its expected applicability for modulation of molecular recognition phenomena in chemistry and biology, halogen bonding has lately attracted rapidly increasing interest. As most of these processes proceed in solution, the understanding of the influence of solvents on the interaction is of utmost importance. In addition, solution studies provide fundamental insights into the nature of halogen bonding, including, for example, the relative importance of charge transfer, dispersion, and electrostatics forces. Herein, a selection of halogen bonding literature is reviewed with the discussion focusing on the solvent effect and the electronic characteristics of halogen bonded complexes. Hence, charged and neutral systems together with two- and three-center bonds are presented in separate sub-sections. Solvent polarity is shown to have a slight stabilizing effect on neutral, two-center halogen bonds while strongly destabilizes charged, two-center complexes. It does not greatly influence the geometry of three-center halogen bonds, even though polar solvents facilitate dissociation of the counter-ion of charged three-center bonds. The charged three-center bonds are strengthened by increased environment polarity. Solvents possessing hydrogen bond donor functionalities efficiently destabilize all types of halogen bonds, primarily because of halogen vs hydrogen bond competition. A purely electrostatic model is insufficient for the description of halogen bonds in polar systems whereas it may give reasonable correlation to experimental data obtained in noninteracting, apolar solvents. Whereas dispersion plays a significant role for neutral, two-center halogen bonds, charged halogen bond complexes possess a significant charge transfer characteristic.

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Symmetry of hydrogen bonds in solution

Cited by 62 publications

References 122 publications

H/D Isotope Effects in Hydrogen Bonded Systems

H/D Isotope Effects in Hydrogen Bonded Systems

Isotope-Induced Desymmetrization Can Mimic Isotopic Perturbation of Equilibria. On the Symmetry of Bromonium Ions and Hydrogen Bonds

Halogen Bonding in Solution

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