Sensitivity of 31P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines

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Sensitivity of ³¹P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines. / Giba, Ivan S.; Mulloyarova, Valeriia V.; Denisov, Gleb S.; Tolstoy, Peter M.

в: Magnetic Resonance in Chemistry, Том 59, № 4, 04.2021, стр. 465-477.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{21f261701cc54794ba9a6b2b42c0ed8c,

title = "Sensitivity of 31P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines",

abstract = "The results of the quantum-chemical investigation of a series of hydrogen-bonded 1:1 acid–base complexes formed by model phosphinic acids, Me2POOH, and PhHPOOH, are reported. A series of substituted pyridines (pKa range from 0.5 to 10) was chosen as proton acceptors. Gradual changes of isotropic 31P nuclear magnetic resonance (NMR) chemical shift, δP, were correlated with the bridging proton position in the intermolecular OHN hydrogen bond, namely, r (OH) distance; the proposed correlation could easily be extended to other phosphinic acids as well. For complexes with pyridine and 2,4,6-trimethylpyridine, we have investigated in more detail several factors influencing the δP values: (1) the proton transfer within the OHN hydrogen bond; (2) the rotation of the pyridine ring around the hydrogen bond axis (associated with the formation/breakage of additional weak P-O···H–C hydrogen bond); and (3) the rotation of the phenyl substituent in phenylphosphinic acid around the P–C axis. All these factors appeared to be of similar magnitude, thus masking their individual contributions that have to be independently estimated for a reliable spectral interpretation.",

keywords = "P NMR, hydrogen bonds, phosphinic acids, pyridines, structure–spectrum correlations, NUCLEAR-MAGNETIC-RESONANCE, spectrum correlations, SOLID-STATE, SOLVENT, P-31 NMR, OHN, SPECTROSCOPY, FLUCTUATIONS, structure&#8211, PROTON-TRANSFER, 31P NMR",

author = "Giba, {Ivan S.} and Mulloyarova, {Valeriia V.} and Denisov, {Gleb S.} and Tolstoy, {Peter M.}",

note = "Publisher Copyright: {\textcopyright} 2020 John Wiley & Sons, Ltd.",

year = "2021",

month = apr,

doi = "10.1002/mrc.5123",

language = "English",

volume = "59",

pages = "465--477",

journal = "Magnetic Resonance in Chemistry",

issn = "0749-1581",

publisher = "Wiley-Blackwell",

number = "4",

}

RIS

TY - JOUR

T1 - Sensitivity of 31P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines

AU - Giba, Ivan S.

AU - Mulloyarova, Valeriia V.

AU - Denisov, Gleb S.

AU - Tolstoy, Peter M.

PY - 2021/4

Y1 - 2021/4

N2 - The results of the quantum-chemical investigation of a series of hydrogen-bonded 1:1 acid–base complexes formed by model phosphinic acids, Me2POOH, and PhHPOOH, are reported. A series of substituted pyridines (pKa range from 0.5 to 10) was chosen as proton acceptors. Gradual changes of isotropic 31P nuclear magnetic resonance (NMR) chemical shift, δP, were correlated with the bridging proton position in the intermolecular OHN hydrogen bond, namely, r (OH) distance; the proposed correlation could easily be extended to other phosphinic acids as well. For complexes with pyridine and 2,4,6-trimethylpyridine, we have investigated in more detail several factors influencing the δP values: (1) the proton transfer within the OHN hydrogen bond; (2) the rotation of the pyridine ring around the hydrogen bond axis (associated with the formation/breakage of additional weak P-O···H–C hydrogen bond); and (3) the rotation of the phenyl substituent in phenylphosphinic acid around the P–C axis. All these factors appeared to be of similar magnitude, thus masking their individual contributions that have to be independently estimated for a reliable spectral interpretation.

AB - The results of the quantum-chemical investigation of a series of hydrogen-bonded 1:1 acid–base complexes formed by model phosphinic acids, Me2POOH, and PhHPOOH, are reported. A series of substituted pyridines (pKa range from 0.5 to 10) was chosen as proton acceptors. Gradual changes of isotropic 31P nuclear magnetic resonance (NMR) chemical shift, δP, were correlated with the bridging proton position in the intermolecular OHN hydrogen bond, namely, r (OH) distance; the proposed correlation could easily be extended to other phosphinic acids as well. For complexes with pyridine and 2,4,6-trimethylpyridine, we have investigated in more detail several factors influencing the δP values: (1) the proton transfer within the OHN hydrogen bond; (2) the rotation of the pyridine ring around the hydrogen bond axis (associated with the formation/breakage of additional weak P-O···H–C hydrogen bond); and (3) the rotation of the phenyl substituent in phenylphosphinic acid around the P–C axis. All these factors appeared to be of similar magnitude, thus masking their individual contributions that have to be independently estimated for a reliable spectral interpretation.

KW - P NMR

KW - hydrogen bonds

KW - phosphinic acids

KW - pyridines

KW - structure–spectrum correlations

KW - NUCLEAR-MAGNETIC-RESONANCE

KW - spectrum correlations

KW - SOLID-STATE

KW - SOLVENT

KW - P-31 NMR

KW - OHN

KW - SPECTROSCOPY

KW - FLUCTUATIONS

KW - structure&#8211

KW - PROTON-TRANSFER

KW - 31P NMR

UR - http://www.scopus.com/inward/record.url?scp=85099059654&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3080becc-6754-3b61-aba0-c58ae42fbae9/

U2 - 10.1002/mrc.5123

DO - 10.1002/mrc.5123

M3 - Article

C2 - 33332667

AN - SCOPUS:85099059654

VL - 59

SP - 465

EP - 477

JO - Magnetic Resonance in Chemistry

JF - Magnetic Resonance in Chemistry

SN - 0749-1581

IS - 4

ER -

ID: 85605439