H-bond acceptor parameters for anions

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H-bond acceptor parameters for anions. / Pike, Sarah; Hutchinson, Jordan J. ; Hunter, Christopher A. .

In: Journal of the American Chemical Society, Vol. 139, No. 19, 17.05.2017, p. 6700-6706.

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Pike, Sarah ; Hutchinson, Jordan J. ; Hunter, Christopher A. . / H-bond acceptor parameters for anions. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 19. pp. 6700-6706.

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@article{068b25596ec64567b8179b1d1b65bfba,
title = "H-bond acceptor parameters for anions",
abstract = "UV/vis absorption titrations have been used to investigate the formation of H-bonded complexes between anionic H-bond acceptors (HBAs) and neutral H-bond donors (HBDs) in organic solvents. Complexes formed by three different HBDs with 15 different anions were studied in chloroform and in acetonitrile. The data were used to determine self-consistent HBA parameters (β) for chloride, bromide, iodide, phosphate diester, acetate, benzoate, perrhenate, nitrate, triflimide, perchlorate, hexafluorophosphate, hydrogen sulfate, methyl sulfonate, triflate, and perfluorobutyl sulfonate. The results demonstrate the transferability of H-bond parameters for anions between different solvents and different HBD partners, allowing reliable prediction of anion recognition properties in other scenarios. Carboxylates are the strongest HBAs studied, with β parameters (≈ 15) that are significantly higher than those of neutral organic HBAs, and the non-coordinating anion hexafluorophosphate is the weakest acceptor, with a β parameter comparable to that of pyridine. The effects of ion pairing with the counter-cation were found to be negligible, provided small polar cations were avoided in the less polar solvent (chloroform). There is no correlation between the H-bonding properties of the anions and the pKa values of the conjugate acids.",
author = "Sarah Pike and Hutchinson, {Jordan J.} and Hunter, {Christopher A.}",
year = "2017",
month = may,
day = "17",
doi = "10.1021/jacs.7b02008",
language = "English",
volume = "139",
pages = "6700--6706",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "19",

}

RIS

TY - JOUR

T1 - H-bond acceptor parameters for anions

AU - Pike, Sarah

AU - Hutchinson, Jordan J.

AU - Hunter, Christopher A.

PY - 2017/5/17

Y1 - 2017/5/17

N2 - UV/vis absorption titrations have been used to investigate the formation of H-bonded complexes between anionic H-bond acceptors (HBAs) and neutral H-bond donors (HBDs) in organic solvents. Complexes formed by three different HBDs with 15 different anions were studied in chloroform and in acetonitrile. The data were used to determine self-consistent HBA parameters (β) for chloride, bromide, iodide, phosphate diester, acetate, benzoate, perrhenate, nitrate, triflimide, perchlorate, hexafluorophosphate, hydrogen sulfate, methyl sulfonate, triflate, and perfluorobutyl sulfonate. The results demonstrate the transferability of H-bond parameters for anions between different solvents and different HBD partners, allowing reliable prediction of anion recognition properties in other scenarios. Carboxylates are the strongest HBAs studied, with β parameters (≈ 15) that are significantly higher than those of neutral organic HBAs, and the non-coordinating anion hexafluorophosphate is the weakest acceptor, with a β parameter comparable to that of pyridine. The effects of ion pairing with the counter-cation were found to be negligible, provided small polar cations were avoided in the less polar solvent (chloroform). There is no correlation between the H-bonding properties of the anions and the pKa values of the conjugate acids.

AB - UV/vis absorption titrations have been used to investigate the formation of H-bonded complexes between anionic H-bond acceptors (HBAs) and neutral H-bond donors (HBDs) in organic solvents. Complexes formed by three different HBDs with 15 different anions were studied in chloroform and in acetonitrile. The data were used to determine self-consistent HBA parameters (β) for chloride, bromide, iodide, phosphate diester, acetate, benzoate, perrhenate, nitrate, triflimide, perchlorate, hexafluorophosphate, hydrogen sulfate, methyl sulfonate, triflate, and perfluorobutyl sulfonate. The results demonstrate the transferability of H-bond parameters for anions between different solvents and different HBD partners, allowing reliable prediction of anion recognition properties in other scenarios. Carboxylates are the strongest HBAs studied, with β parameters (≈ 15) that are significantly higher than those of neutral organic HBAs, and the non-coordinating anion hexafluorophosphate is the weakest acceptor, with a β parameter comparable to that of pyridine. The effects of ion pairing with the counter-cation were found to be negligible, provided small polar cations were avoided in the less polar solvent (chloroform). There is no correlation between the H-bonding properties of the anions and the pKa values of the conjugate acids.

U2 - 10.1021/jacs.7b02008

DO - 10.1021/jacs.7b02008

M3 - Article

VL - 139

SP - 6700

EP - 6706

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 19

ER -