Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
H/D isotope effects on 1H-NMR chemical shifts in cyclic heterodimers and heterotrimers of phosphinic and phosphoric acids. / Mulloyarova, Valeriia V.; Ustimchuk, Daria O.; Filarowski, Aleksander; Tolstoy, Peter M.
в: Molecules, Том 25, № 8, 1907, 02.04.2020.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - H/D isotope effects on 1H-NMR chemical shifts in cyclic heterodimers and heterotrimers of phosphinic and phosphoric acids
AU - Mulloyarova, Valeriia V.
AU - Ustimchuk, Daria O.
AU - Filarowski, Aleksander
AU - Tolstoy, Peter M.
PY - 2020/4/2
Y1 - 2020/4/2
N2 - Hydrogen-bonded heterocomplexes formed by POOH-containing acids (diphenylphosphoric 1, dimethylphosphoric 2, diphenylphosphinic 3, and dimethylphosphinic 4) are studied by the low-temperature (100 K) 1H-NMR and 31P-NMR using liquefied gases CDF3/CDF2Cl as a solvent. Formation of cyclic dimers and cyclic trimers consisting of molecules of two different acids is confirmed by the analysis of vicinal H/D isotope effects (changes in the bridging proton chemical shift, δH, after the deuteration of a neighboring H-bond). Acids 1 and 4 (or 1 and 3) form heterotrimers with very strong (short) H-bonds (δH ca. 17 ppm). While in the case of all heterotrimers the H-bonds are cyclically arranged head-to-tail, ···O=P–O–H···O=P–O–H···, and thus their cooperative coupling is expected, the signs of vicinal H/D isotope effects indicate an effective anticooperativity, presumably due to steric factors: when one of the H-bonds is elongated upon deuteration, the structure of the heterotrimer adjusts by shortening the neighboring hydrogen bonds. We also demonstrate the formation of cyclic tetramers: in the case of acids 1 and 4 the structure has alternating molecules of 1 and 4 in the cycle, while in case of acids 1 and 3 the cycle has two molecules of 1 followed by two molecules of 3.
AB - Hydrogen-bonded heterocomplexes formed by POOH-containing acids (diphenylphosphoric 1, dimethylphosphoric 2, diphenylphosphinic 3, and dimethylphosphinic 4) are studied by the low-temperature (100 K) 1H-NMR and 31P-NMR using liquefied gases CDF3/CDF2Cl as a solvent. Formation of cyclic dimers and cyclic trimers consisting of molecules of two different acids is confirmed by the analysis of vicinal H/D isotope effects (changes in the bridging proton chemical shift, δH, after the deuteration of a neighboring H-bond). Acids 1 and 4 (or 1 and 3) form heterotrimers with very strong (short) H-bonds (δH ca. 17 ppm). While in the case of all heterotrimers the H-bonds are cyclically arranged head-to-tail, ···O=P–O–H···O=P–O–H···, and thus their cooperative coupling is expected, the signs of vicinal H/D isotope effects indicate an effective anticooperativity, presumably due to steric factors: when one of the H-bonds is elongated upon deuteration, the structure of the heterotrimer adjusts by shortening the neighboring hydrogen bonds. We also demonstrate the formation of cyclic tetramers: in the case of acids 1 and 4 the structure has alternating molecules of 1 and 4 in the cycle, while in case of acids 1 and 3 the cycle has two molecules of 1 followed by two molecules of 3.
KW - H/D isotope effects
KW - Heterodimers
KW - Heterotetramers
KW - Heterotrimers
KW - Hydrogen bond
KW - NMR
KW - Phosphinic acids
KW - Phosphoric acids
KW - heterotrimers
KW - HYDROGEN-BOND
KW - heterotetramers
KW - CRYSTAL-STRUCTURE
KW - PHASE ELECTRON-DIFFRACTION
KW - PROTON
KW - heterodimers
KW - DIMERS
KW - ACETIC-ACID
KW - phosphinic acids
KW - SOLVENT
KW - phosphoric acids
KW - GAS-PHASE
KW - hydrogen bond
KW - CARBOXYLIC-ACIDS
UR - http://www.scopus.com/inward/record.url?scp=85083557255&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/daae739a-ac8e-3a13-b73c-4bac235099e9/
U2 - 10.3390/molecules25081907
DO - 10.3390/molecules25081907
M3 - Article
C2 - 32326122
AN - SCOPUS:85083557255
VL - 25
JO - Molecules
JF - Molecules
SN - 1420-3049
IS - 8
M1 - 1907
ER -
ID: 53584473