New look at the Badger-Bauer rule: Correlations of spectroscopic IR and NMR parameters with hydrogen bond energy and geometry. FHF complexes

Tupikina, Elena Yu.; Денисов, Г. С.; Меликова, С.М.; Kucherov, S. Yu.; Tolstoy, Peter M.

doi:10.1016/j.molstruc.2018.03.018

Cited by 24 publications

(19 citation statements)

References 92 publications

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“…Correlations between hydrogen‐bond strength and spectroscopic parameters go back to Badger and Bauer's work of 1937 on the vibrational spectra of hydrogen‐bonded complexes between alcohols and various solvents . NMR spectral shift enhancement is recognised as a criterion of hydrogen bonding, and many correlations between shifts and different measures of the hydrogen‐bond strength, not only in complexes but also related to intramolecular interactions, have been proposed. Such correlations have been used to infer hydrogen‐bond strengths or distances from spectroscopic data.…”

Section: Discussionmentioning

confidence: 99%

“…The question arises as to what measure of the bond strength is appropriate for these correlations. Hydrogen‐bond energies, enthalpies, binding energies, and heats of formation, determined by various approaches, have been frequently used, as well as correlations with bond length, it being tacitly or explicitly accepted that energy and bond length are correlated. In the context of QTAIM analysis, when there is a BCP associated with the hydrogen bond, other properties, such as the electron density, ρ, its Laplacian, ∇ 2 ρ, and the potential‐energy density, V, have been exploited .…”

Section: Discussionmentioning

confidence: 99%

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Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Lomas

2019

Magnetic Reson in Chemistry

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Hydrogen-hydrogen C─H … H─C bonding between the bay-area hydrogens in biphenyls, and more generally in congested alkanes, very strained polycyclic alkanes, and cis-2-butene, has been investigated by calculation of proton nuclear magnetic resonance (NMR) shifts and atom-atom interaction energies.Computed NMR shifts for all protons in the biphenyl derivatives correlate very well with experimental data, with zero intercept, unit slope, and a root mean square deviation of 0.06 ppm. For some congested alkanes, there is generally good agreement between computed values for a selected conformer and the experimental data, when it is available. In both cases, the shift of a given proton or pair of protons tends to increase with the corresponding interaction energy. Computed NMR shift differences for methylene protons in polycyclic alkanes, where one is involved in a very short contact ("in") and the other is not ("out"), show a rough correlation with the corresponding C─H … H─C exchange energies. The "in" and "in,in" isomers of selected aza-and diazacycloalkanes, respectively, are X─H … H─N hydrogen bonded, whereas the "out" and "in,out" isomers display X─H … N hydrogen bonds (X = C or N).Oxa-alkanes and the "in" isomers of aza-oxa-alkanes are X─H … O hydrogen bonded. There is a very good general correlation, including both N─H … H─Y (Y = C or N) and N─H … Z (Z = N or O) interactions, for NH proton shifts against the exchange energy. For "in" CH protons, the data for the different C─H … H─Y and C─H … Z interactions are much more dispersed and the overall shift/exchange energy correlation is less satisfactory.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Lomas

2019

Magnetic Reson in Chemistry

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“…Similar calculations with lighter (kaon) or heavier (T, 7 H) particles (see Table S4) demonstrate that further mass change does not lead to any meaningful changes in ν FH . In other words, the stretching frequency ν FH of a single FH molecule could be considered as a characteristic vibrational frequency (“local mode”).…”

Section: Resultsmentioning

confidence: 99%

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

2019

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The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH) nCl]− (n = 1…6) was calculated (CCSD/aug‐cc‐pVDZ) and compared with [(FH) nF]− clusters. The geometry is determined by the symmetry‐driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ‐hole), which limits the range of directions available for subsequent H‐bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H‐bonds by 23–16% and decreases their covalent character (as seen by LMO‐EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl. © 2019 Wiley Periodicals, Inc.

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“…However, often MESP and ELF functions reach their extreme values at relatively small distances of about ~0.5–1.0 Å from the atom center, while at larger distances the corresponding 3D maps quickly become rather featureless. Another way to map outer electronic shell is to use a probe atom or molecule, whose spectroscopic observables could be correlated with electron shell features . The probe, interacting noncovalently with the studied molecule, is typically located at larger distances from the atomic centers, that is, in the region specifically relevant for such interactions.…”

Section: Introductionmentioning

confidence: 99%

“…For example in Ref. 3 He nucleus was used for investigation of carbon systems (fullerenes, nanotubes, graphene). Furthermore, the surface characteristics of aerogel, PrF 3 nanoparticles, and geological samples of calcium carbonate, were studied by relaxation properties of 3 He.…”

Section: Introductionmentioning

confidence: 99%

Outer electronic shell visualization by NMR chemical shift laplacian of a helium probe

et al. 2018

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A new method of visualization of lone pairs is proposed using fluorine atoms in fluoroacetylene, trifluoroethylene, and fluoroform (sp, sp 2 , and sp 3 hybridized carbons) as an example. The space around fluorines was probed by a helium atom and at each point 3 He NMR chemical shift δ He and its Laplacian r 2 δ He were calculated. The r 2 δ He isosurfaces have symmetrical toroidal shapes along CF axes; the maximum values of r 2 δ He are reached at about 1.5 Å from fluorine atom center in the direction roughly coinciding with the lone pair localization. The absolute values of the r 2 δ He could be used to quantify the electron-rich regions of lone pairs. The results are compared with more common visualization methods-3D maps of the molecular electrostatic potential and the electron localization function. We show that a helium atom could be used for evaluation of fine features of molecular electronic shell, since 3 He NMR spectral characteristics remain sensitive at relatively large distances.

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New look at the Badger-Bauer rule: Correlations of spectroscopic IR and NMR parameters with hydrogen bond energy and geometry. FHF complexes

Cited by 24 publications

References 92 publications

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Outer electronic shell visualization by NMR chemical shift laplacian of a helium probe

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New look at the Badger-Bauer rule: Correlations of spectroscopic IR and NMR parameters with hydrogen bond energy and geometry. FHF complexes

Cited by 24 publications

References 92 publications

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H…H─Y and X─H…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H…H─Y and X─H…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

Outer electronic shell visualization by NMR chemical shift laplacian of a helium probe

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About

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Relationships between NMR shifts and interaction energies in biphenyls, alkanes, aza‐alkanes, and oxa‐alkanes with X─H^…H─Y and X─H^…Z (X, Y = C or N; Z = N or O) hydrogen bonding

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)