Influence of Hydrogen Bonds in 1:1 Complexes of Phosphinic Acids with Substituted Pyridines on 1H and 31P NMR Chemical Shifts

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Abstract

Two series of 1:1 complexes with strong OHN hydrogen bonds formed by dimethylphosphinic and phenylphosphinic acids with 10 substituted pyridines were studied experimentally by liquid state NMR spectroscopy at 100 K in solution in a low-freezing polar aprotic solvent mixture CDF 3 /CDClF 2 . The hydrogen bond geometries were estimated using previously established correlations linking 1 H NMR chemical shifts of bridging protons with the O···H and H···N interatomic distances. A new correlation is proposed allowing one to estimate the interatomic distance within the OHN bridge from the displacement of 31 P NMR signal upon complexation. We show that the values of 31 P NMR chemical shifts are affected by an additional CH···O hydrogen bond formed between the P?O group of the acid and ortho-CH proton of the substituted pyridines. Breaking of this bond in the case of 2,6-disubstituted bases shifts the 31 P NMR signal by ca. 1.5 ppm to the high field.

Original languageEnglish
Pages (from-to)2252-2260
JournalJournal of Physical Chemistry A
Volume123
Issue number11
Early online date26 Feb 2019
DOIs
Publication statusPublished - 21 Mar 2019

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Phosphinic Acids
Pyridines
Chemical shift
chemical equilibrium
pyridines
Hydrogen bonds
Nuclear magnetic resonance
hydrogen bonds
nuclear magnetic resonance
acids
Protons
Complexation
Freezing
protons
Nuclear magnetic resonance spectroscopy
freezing
Acids
Geometry
methylidyne
Liquids

Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Influence of Hydrogen Bonds in 1:1 Complexes of Phosphinic Acids with Substituted Pyridines on 1H and 31P NMR Chemical Shifts",
abstract = "Two series of 1:1 complexes with strong OHN hydrogen bonds formed by dimethylphosphinic and phenylphosphinic acids with 10 substituted pyridines were studied experimentally by liquid state NMR spectroscopy at 100 K in solution in a low-freezing polar aprotic solvent mixture CDF 3 /CDClF 2 . The hydrogen bond geometries were estimated using previously established correlations linking 1 H NMR chemical shifts of bridging protons with the O···H and H···N interatomic distances. A new correlation is proposed allowing one to estimate the interatomic distance within the OHN bridge from the displacement of 31 P NMR signal upon complexation. We show that the values of 31 P NMR chemical shifts are affected by an additional CH···O hydrogen bond formed between the P?O group of the acid and ortho-CH proton of the substituted pyridines. Breaking of this bond in the case of 2,6-disubstituted bases shifts the 31 P NMR signal by ca. 1.5 ppm to the high field.",
keywords = "CRYSTAL-STRUCTURE, CYCLIC DIMER, GAS-PHASE, HINDERED SOLVENT EXTRACTANTS, MOLECULAR-STRUCTURE, N-15 NMR, PHASE ELECTRON-DIFFRACTION, PHOSPHORIC-ACID, PROTON-TRANSFER, SOLID-STATE",
author = "Giba, {Ivan S.} and Mulloyarova, {Valeria V.} and Denisov, {Gleb S.} and Tolstoy, {Peter M.}",
year = "2019",
month = "3",
day = "21",
doi = "10.1021/acs.jpca.9b00625",
language = "English",
volume = "123",
pages = "2252--2260",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Influence of Hydrogen Bonds in 1:1 Complexes of Phosphinic Acids with Substituted Pyridines on 1H and 31P NMR Chemical Shifts

AU - Giba, Ivan S.

AU - Mulloyarova, Valeria V.

AU - Denisov, Gleb S.

AU - Tolstoy, Peter M.

PY - 2019/3/21

Y1 - 2019/3/21

N2 - Two series of 1:1 complexes with strong OHN hydrogen bonds formed by dimethylphosphinic and phenylphosphinic acids with 10 substituted pyridines were studied experimentally by liquid state NMR spectroscopy at 100 K in solution in a low-freezing polar aprotic solvent mixture CDF 3 /CDClF 2 . The hydrogen bond geometries were estimated using previously established correlations linking 1 H NMR chemical shifts of bridging protons with the O···H and H···N interatomic distances. A new correlation is proposed allowing one to estimate the interatomic distance within the OHN bridge from the displacement of 31 P NMR signal upon complexation. We show that the values of 31 P NMR chemical shifts are affected by an additional CH···O hydrogen bond formed between the P?O group of the acid and ortho-CH proton of the substituted pyridines. Breaking of this bond in the case of 2,6-disubstituted bases shifts the 31 P NMR signal by ca. 1.5 ppm to the high field.

AB - Two series of 1:1 complexes with strong OHN hydrogen bonds formed by dimethylphosphinic and phenylphosphinic acids with 10 substituted pyridines were studied experimentally by liquid state NMR spectroscopy at 100 K in solution in a low-freezing polar aprotic solvent mixture CDF 3 /CDClF 2 . The hydrogen bond geometries were estimated using previously established correlations linking 1 H NMR chemical shifts of bridging protons with the O···H and H···N interatomic distances. A new correlation is proposed allowing one to estimate the interatomic distance within the OHN bridge from the displacement of 31 P NMR signal upon complexation. We show that the values of 31 P NMR chemical shifts are affected by an additional CH···O hydrogen bond formed between the P?O group of the acid and ortho-CH proton of the substituted pyridines. Breaking of this bond in the case of 2,6-disubstituted bases shifts the 31 P NMR signal by ca. 1.5 ppm to the high field.

KW - CRYSTAL-STRUCTURE

KW - CYCLIC DIMER

KW - GAS-PHASE

KW - HINDERED SOLVENT EXTRACTANTS

KW - MOLECULAR-STRUCTURE

KW - N-15 NMR

KW - PHASE ELECTRON-DIFFRACTION

KW - PHOSPHORIC-ACID

KW - PROTON-TRANSFER

KW - SOLID-STATE

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UR - http://www.mendeley.com/research/influence-hydrogen-bonds-11-complexes-phosphinic-acids-substituted-pyridines-1-h-31-p-nmr-chemical-s

U2 - 10.1021/acs.jpca.9b00625

DO - 10.1021/acs.jpca.9b00625

M3 - Article

VL - 123

SP - 2252

EP - 2260

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 11

ER -