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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F19%3A10396290" target="_blank" >RIV/00216208:11320/19:10396290 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=xoGvFQxlgz" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=xoGvFQxlgz</a>

DOI - Digital Object Identifier

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

Jazyk výsledku

angličtina

Název v původním jazyce

Structural interpretation of the P-31 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 P-31 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 &quot;opened&quot; PT and P molecules contrasted with notably different geometries and confined dynamical motions within the cPT and cP &quot;closed&quot; 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 P-31 NMR shifts. The theoretical calculations enabled accurate and reliable structure-dynamical interpretation of the measured P-31 NMR shifts. The effects due to explicit solvent and relativity turned out to be indispensable for obtaining accurate P-31 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 P-31 NMR chemical shifts in thiophosphate and phosphate: key effects due to spin-orbit and explicit solvent

Popis výsledku anglicky

Structural interpretation of the P-31 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 &quot;opened&quot; PT and P molecules contrasted with notably different geometries and confined dynamical motions within the cPT and cP &quot;closed&quot; 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 P-31 NMR shifts. The theoretical calculations enabled accurate and reliable structure-dynamical interpretation of the measured P-31 NMR shifts. The effects due to explicit solvent and relativity turned out to be indispensable for obtaining accurate P-31 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

2019

Číslo periodika v rámci svazku

21

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