Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO H A hydrogen bonds

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Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO H A hydrogen bonds. / Kostin, Mikhail A.; Pylaeva, Svetlana A.; Tolstoy, Peter M.

In: Physical Chemistry Chemical Physics, Vol. 24, No. 11, 25.02.2022, p. 7121-7133.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{a44a4a6a3a444f5293ada75fcc683559,

title = "Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO H A hydrogen bonds",

abstract = "In this work we evaluate the possibility of using the NMR and IR spectral properties of the P =O group to estimate the geometry and strength of hydrogen bonds which it forms with OH-, NH-And CH-Acids. The results of the DFT study of 70 hydrogen-bonded 1: 1 complexes of a model trimethylphosphine oxide, Me3PO, with various proton donors in the gas phase and in aprotic medium (modelled as a polarizable continuum) are presented. Four types of hydrogen bonds with the general formula Me3PO{\^a}H-A were considered, where the A atom is O, C, and N (neutral or cationic acids). Within the selected set of complexes the hydrogen bond energy varies over a wide range (ca. 0-85 kJ mol-1). We show that it is possible to use simple correlations to estimate the energy and geometry of OHO, NHO and CHO hydrogen bonds from the changes of isotropic 31P NMR chemical shifts and harmonic PO stretching vibration frequencies upon complexation. Such correlations also could be used to estimate the proton-donating ability (and Br{\o}nsted acidity; pKa) of OH acids. ",

keywords = "CYCLOTRON RESONANCE DETERMINATION, ELECTRON-DENSITY PROPERTIES, CHEMICAL-SHIFTS, PROTON-TRANSFER, GAS-PHASE, TRIETHYLPHOSPHINE OXIDE, TRANSFER EQUILIBRIUM, MOLECULAR-STRUCTURE, BRONSTED ACIDS, ISOTOPE",

author = "Kostin, {Mikhail A.} and Pylaeva, {Svetlana A.} and Tolstoy, {Peter M.}",

note = "Publisher Copyright: {\textcopyright} the Owner Societies 2022.",

year = "2022",

month = feb,

day = "25",

doi = "10.1039/d1cp05939d",

language = "English",

volume = "24",

pages = "7121--7133",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "11",

}

RIS

TY - JOUR

T1 - Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO H A hydrogen bonds

AU - Kostin, Mikhail A.

AU - Pylaeva, Svetlana A.

AU - Tolstoy, Peter M.

N1 - Publisher Copyright: © the Owner Societies 2022.

PY - 2022/2/25

Y1 - 2022/2/25

N2 - In this work we evaluate the possibility of using the NMR and IR spectral properties of the P =O group to estimate the geometry and strength of hydrogen bonds which it forms with OH-, NH-And CH-Acids. The results of the DFT study of 70 hydrogen-bonded 1: 1 complexes of a model trimethylphosphine oxide, Me3PO, with various proton donors in the gas phase and in aprotic medium (modelled as a polarizable continuum) are presented. Four types of hydrogen bonds with the general formula Me3POâH-A were considered, where the A atom is O, C, and N (neutral or cationic acids). Within the selected set of complexes the hydrogen bond energy varies over a wide range (ca. 0-85 kJ mol-1). We show that it is possible to use simple correlations to estimate the energy and geometry of OHO, NHO and CHO hydrogen bonds from the changes of isotropic 31P NMR chemical shifts and harmonic PO stretching vibration frequencies upon complexation. Such correlations also could be used to estimate the proton-donating ability (and Brønsted acidity; pKa) of OH acids.

AB - In this work we evaluate the possibility of using the NMR and IR spectral properties of the P =O group to estimate the geometry and strength of hydrogen bonds which it forms with OH-, NH-And CH-Acids. The results of the DFT study of 70 hydrogen-bonded 1: 1 complexes of a model trimethylphosphine oxide, Me3PO, with various proton donors in the gas phase and in aprotic medium (modelled as a polarizable continuum) are presented. Four types of hydrogen bonds with the general formula Me3POâH-A were considered, where the A atom is O, C, and N (neutral or cationic acids). Within the selected set of complexes the hydrogen bond energy varies over a wide range (ca. 0-85 kJ mol-1). We show that it is possible to use simple correlations to estimate the energy and geometry of OHO, NHO and CHO hydrogen bonds from the changes of isotropic 31P NMR chemical shifts and harmonic PO stretching vibration frequencies upon complexation. Such correlations also could be used to estimate the proton-donating ability (and Brønsted acidity; pKa) of OH acids.

KW - CYCLOTRON RESONANCE DETERMINATION

KW - ELECTRON-DENSITY PROPERTIES

KW - CHEMICAL-SHIFTS

KW - PROTON-TRANSFER

KW - GAS-PHASE

KW - TRIETHYLPHOSPHINE OXIDE

KW - TRANSFER EQUILIBRIUM

KW - MOLECULAR-STRUCTURE

KW - BRONSTED ACIDS

KW - ISOTOPE

UR - http://www.scopus.com/inward/record.url?scp=85127199371&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/ebb1e9b8-7dbf-3537-91b0-707814dc8e69/

U2 - 10.1039/d1cp05939d

DO - 10.1039/d1cp05939d

M3 - Article

AN - SCOPUS:85127199371

VL - 24

SP - 7121

EP - 7133

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 11

ER -

ID: 94249563