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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2019

Confidentiality

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

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Volume of the periodical

2019

Issue of the periodical within the volume

21

Country of publishing house

GB - UNITED KINGDOM

Number of pages

11

Pages from-to

9924-9934

UT code for WoS article

000473071200027

EID of the result in the Scopus database

2-s2.0-85065988922