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Article

Z,E-Isomerism in a Series of Substituted Iminophosphonates: Quantum Chemical Research

1
Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Murmans’ka Str. 5, 02094 Kyiv, Ukraine
2
National Technical University of Ukraine “Kyiv Polytechnic Institute named after Igor Sikorsky”, Peremogy Ave. 37, 03056 Kyiv, Ukraine
3
Technical Center of the National Academy of Sciences of Ukraine, Pokrovs’ka Str. 13, 04070 Kyiv, Ukraine
4
Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA
*
Authors to whom correspondence should be addressed.
Academic Editor: Tomasz K. Olszewski
Received: 8 March 2021 / Revised: 16 April 2021 / Accepted: 20 April 2021 / Published: 23 April 2021
Esters of iminophosphonic acids (iminophosphonates, or IPs), including a fragment, >P(=O)-C=N, can be easily functionalized, for instance to aminophosphonic acids with a wide range of biological activity. Depending on the character of the substitution, the Z- or E-configuration is favorable for IPs, which in turn can influence the stereochemistry of the products of chemical transformations of IPs. While the Z,E-isomerism in IPs has been thoroughly studied by NMR spectroscopy, the factors stabilizing a definite isomer are still not clear. In the current work, density functional theory (DFT, using M06-2X functional) and ab initio spin-component–scaled second-order Møller–Plesset perturbation theory (SCS-MP2) calculations were carried out for a broad series of IPs. The calculations reproduce well a subtle balance between the preferred Z-configuration inherent for C-trifluoromethyl substituted IPs and the E-form, which is more stable for C-alkyl- or aryl-substituted IPs. The predicted trend of changing activation energy values agrees well with the recently determined experimental ΔG298 magnitudes. Depending on the substitution in the aromatic moiety, the Z/E-isomerization of N-aryl-substituted IPs proceeds via two types of close-in energy transition states. Not a single main factor but a combination of various contributions should be considered in order to explain the Z/E-isomerization equilibrium for different IPs. View Full-Text
Keywords: DFT calculations; SCS-MP2 calculations; Z,E-isomerism; iminophosphonates; thermodynamic stability DFT calculations; SCS-MP2 calculations; Z,E-isomerism; iminophosphonates; thermodynamic stability
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MDPI and ACS Style

Rozhenko, A.B.; Kyrylchuk, A.A.; Lapinska, Y.O.; Rassukana, Y.V.; Trachevsky, V.V.; Pirozhenko, V.V.; Leszczynski, J.; Onysko, P.P. Z,E-Isomerism in a Series of Substituted Iminophosphonates: Quantum Chemical Research. Organics 2021, 2, 84-97. https://0-doi-org.brum.beds.ac.uk/10.3390/org2020008

AMA Style

Rozhenko AB, Kyrylchuk AA, Lapinska YO, Rassukana YV, Trachevsky VV, Pirozhenko VV, Leszczynski J, Onysko PP. Z,E-Isomerism in a Series of Substituted Iminophosphonates: Quantum Chemical Research. Organics. 2021; 2(2):84-97. https://0-doi-org.brum.beds.ac.uk/10.3390/org2020008

Chicago/Turabian Style

Rozhenko, Alexander B., Andrey A. Kyrylchuk, Yuliia O. Lapinska, Yuliya V. Rassukana, Vladimir V. Trachevsky, Volodymyr V. Pirozhenko, Jerzy Leszczynski, and Petro P. Onysko 2021. "Z,E-Isomerism in a Series of Substituted Iminophosphonates: Quantum Chemical Research" Organics 2, no. 2: 84-97. https://0-doi-org.brum.beds.ac.uk/10.3390/org2020008

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