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Structural interpretation of the 31P NMR chemical shifts in thiophosphate and phosphate: key effects due to spin-orbit and explicit solvent

Identifikátory výsledku

  • Kód výsledku v IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F19%3A00507296" target="_blank" >RIV/61388963:_____/19:00507296 - isvavai.cz</a>

  • Nalezeny alternativní kódy

    RIV/68407700:21230/19:00338431

  • Výsledek na webu

    <a href="https://pubs.rsc.org/en/content/articlelanding/2019/CP/C9CP01460H#!divAbstract" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2019/CP/C9CP01460H#!divAbstract</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1039/c9cp01460h" target="_blank" >10.1039/c9cp01460h</a>

Alternativní jazyky

  • Jazyk výsledku

    angličtina

  • Název v původním jazyce

    Structural interpretation of the 31P NMR chemical shifts in thiophosphate and phosphate: key effects due to spin-orbit and explicit solvent

  • Popis výsledku v původním jazyce

    Structural interpretation of the 31P NMR shifts measured in O,O-diethyl thiophosphate (PT), 5,5-dimethyl-2- mercapto-1,3,2-dioxaphosphorinane 2-oxide (cPT), diethylphosphate (P) and 5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphinane 2-oxide (cP) was obtained by means of theoretical calculations including the effects of geometry, molecular dynamics, and solvent, relativistic effects and the effect of NMR reference. NMR calculations employed the B3LYP, BP86, BPW91, M06-2X, PBE0, MP2, and HF methods, the Iglo-n (n = II, III), cc-pVnZ (n = D, T, Q, 5), and pcS-n (n = 0, 1, 2, 3, 4) Gaussian-type basis sets and the Slatertype QZ4P atomic basis. Water solvent was described explicitly and/or implicitly. The effects due to molecular dynamics were calculated using molecular dynamics simulations with the GAFF force field and the TIP3P water molecules, and alternatively by means of the zero-point ro-vibrational averaging. Relativistic effects included the spin-orbit calculated within the two-component zero-order relativistic approximation and the effect with the four-component DFT method. Optimal geometries and largeamplitude dynamical motions within the “opened” PT and P molecules contrasted with notably different geometries and confined dynamical motions within the cPT and cP “closed” molecules. These structuredynamical differences together with the different chemical structures of thiophosphate and phosphate due to a non-esterified sulphur or oxygen atom within the group considerably affected the magnitudes of 31P NMR shifts. The theoretical calculations enabled accurate and reliable structure-dynamical interpretation of the measured 31P NMR shifts. The effects due to explicit solvent and relativity turned out to be indispensable for obtaining accurate 31P NMR shifts particularly in the thiophosphates. Replacement of the non-esterified oxygen atom in the phosphate with sulphur makes NMR shielding of the phosphorus atom qualitatively different as compared to the NMR shielding of the phosphorus atom in phosphate, H3PO4 and PH3.

  • Název v anglickém jazyce

    Structural interpretation of the 31P NMR chemical shifts in thiophosphate and phosphate: key effects due to spin-orbit and explicit solvent

  • Popis výsledku anglicky

    Structural interpretation of the 31P NMR shifts measured in O,O-diethyl thiophosphate (PT), 5,5-dimethyl-2- mercapto-1,3,2-dioxaphosphorinane 2-oxide (cPT), diethylphosphate (P) and 5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphinane 2-oxide (cP) was obtained by means of theoretical calculations including the effects of geometry, molecular dynamics, and solvent, relativistic effects and the effect of NMR reference. NMR calculations employed the B3LYP, BP86, BPW91, M06-2X, PBE0, MP2, and HF methods, the Iglo-n (n = II, III), cc-pVnZ (n = D, T, Q, 5), and pcS-n (n = 0, 1, 2, 3, 4) Gaussian-type basis sets and the Slatertype QZ4P atomic basis. Water solvent was described explicitly and/or implicitly. The effects due to molecular dynamics were calculated using molecular dynamics simulations with the GAFF force field and the TIP3P water molecules, and alternatively by means of the zero-point ro-vibrational averaging. Relativistic effects included the spin-orbit calculated within the two-component zero-order relativistic approximation and the effect with the four-component DFT method. Optimal geometries and largeamplitude dynamical motions within the “opened” PT and P molecules contrasted with notably different geometries and confined dynamical motions within the cPT and cP “closed” molecules. These structuredynamical differences together with the different chemical structures of thiophosphate and phosphate due to a non-esterified sulphur or oxygen atom within the group considerably affected the magnitudes of 31P NMR shifts. The theoretical calculations enabled accurate and reliable structure-dynamical interpretation of the measured 31P NMR shifts. The effects due to explicit solvent and relativity turned out to be indispensable for obtaining accurate 31P NMR shifts particularly in the thiophosphates. Replacement of the non-esterified oxygen atom in the phosphate with sulphur makes NMR shielding of the phosphorus atom qualitatively different as compared to the NMR shielding of the phosphorus atom in phosphate, H3PO4 and PH3.

Klasifikace

  • Druh

    J<sub>imp</sub> - Článek v periodiku v databázi Web of Science

  • CEP obor

  • OECD FORD obor

    10403 - Physical chemistry

Návaznosti výsledku

  • Projekt

    <a href="/cs/project/GA19-13436S" target="_blank" >GA19-13436S: Nový vhled do struktury a dynamiky páteře nukleových kyselin užitím pokročilých DFT-MD výpočtů a 31P NMR spektroskopie</a><br>

  • Návaznosti

    I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Ostatní

  • Rok uplatnění

    2019

  • Kód důvěrnosti údajů

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Údaje specifické pro druh výsledku

  • Název periodika

    Physical Chemistry Chemical Physics

  • ISSN

    1463-9076

  • e-ISSN

  • Svazek periodika

    21

  • Číslo periodika v rámci svazku

    19

  • Stát vydavatele periodika

    GB - Spojené království Velké Británie a Severního Irska

  • Počet stran výsledku

    11

  • Strana od-do

    9924-9934

  • Kód UT WoS článku

    000473071200027

  • EID výsledku v databázi Scopus

    2-s2.0-85065988922