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Interaction of 1,3,5-Triaryl-1,3,5-Triazacyclohexantricarcarbonyl Complexes of Tung-sten and Chromium with Diethyl H-Phosphonate: Theoretical and Experimental Study

A.V. Plotnikova*, E.V. Kolpakova**, A.I. Kuramshin***, V.I. Galkin****

Kazan Federal University, Kazan, 420008 Russia

E-mail: *anezka_93@mail.ru, **argironet@gmail.com, ***fea_naro@mail.ru, ****Vladimir.Galkin@kpfu.ru

Received January 18, 2017

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Abstract

Experimentally and with the help of quantum chemical calculations (density functional theory, B3LYP/LANL2DZ), the interaction of diethylphosphite with 1,3,5-triaryl-1,3,5-triazacyclohexanetri­carbonylmetals(0) has been studied. It has been shown that the formation of a phosphoorganometallic derivative where the phosphorus atom of diethyl-H-phosphonate remains in the tetravalent four-coordinated state and diethyl-H-phosphonate stays in the hydroxy-tautomeric form stabilized by the interaction of the phosphorus atom lone electron pair with the transition metal is most advantageous. In accordance with the results of quantum chemical calculations, the hydrogen of the hydroxyl group of the phosphoorganometallic compound is mobile and capable of heterolysis, which indicates the possibility of participation of the resulting phosphoorganometallic compound in the electrophilic version of the Pudovik reaction. The detected ability of 1,3,5-triaryl-1,3,5-triazacyclohexanetricarbonyltungstens(0) to catalyze the addition of diethyl-H-phosphonate to methylphenylacetylene confirms this assumption.

Keywords: quantum chemical calculations, organic derivatives of chromium group metals, density functional (DFT), 1,3,5-triaryl-1,3,5-triazacyclohexanes, hydrophosphoryl compounds, hydroxy-tautomeric form of dialkylphosphite, catalysis

Figure Captions

Fig. 1. The reactions modelled using the quantum chemical methods of the metal complex and diethyl­phosphite accompanied by the elimination of one or two СО molecules.

Fig. 2. The reactions modelled using the quantum chemical methods of the metal complex and diethyl­phosphite accompanied by changes in the topology of binding between the triazine ligand and the metal center.

Fig. 3. The calculated (B3LYP/LANL2Z) energies of formation of the model products of interaction of (phtach)Mo(CO)3 complex with dialkyl phosphite (СО elimination).

Fig. 4. The calculated (B3LYP/LANL2Z) energies of formation of the model products of interaction of (phtach)Mo(CO)3 complex with dialkyl phosphite (haptotropic rearrangement of the triazine ligand).

Fig. 5. The calculated (B3LYP/LANL2Z) energies of formation of the model products of interaction of (phtach)W(CO)3 complex with dialkyl phosphite (СО elimination).

Fig. 6. The calculated (B3LYP/LANL2Z) energies of formation of the model products of interaction of (phtach)W(CO)3 complex with dialkyl phosphite (haptotropic rearrangement of the triazine ligand).

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For citation: Plotnikova A.V., Kolpakova E.V., Kuramshin A.I., Galkin V.I. Interaction of 1,3,5-triaryl-1,3,5-triazacyclohexantricarcarbonyl complexes of tungsten and chromium with diethyl H-phosphonate: Theoretical and experimental study. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2017, vol. 159, no. 1, pp. 21–39. (In Russian)


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Interaction of 1,3,5-Triaryl-1,3,5-Triazacyclohexantricarcarbonyl Complexes of Tung-sten and Chromium with Diethyl H-Phosphonate: Theoretical and Experimental Study