Stereochemistry of the cis-Tetrafluoro Complexes of Titanium with 1-Ac-2-[Ph2P(O)]-Cyclohexane (1RS,2SR) Stereoisomers in СН2Сl2

E. G. Il’in; Ильин Е. Г.; A. S. Parshakov; Паршаков А. С.; V. I. Privalov; Привалов В. И.; A. V. Churakov; Чураков А. В.; G. V. Bodrin; Бодрин Г. В.; E. I. Goryunov; Горюнов Е. И.

doi:10.31857/S0132344X24020032

Stereochemistry of the cis-Tetrafluoro Complexes of Titanium with 1-Ac-2-[Ph2P(O)]-Cyclohexane (1RS,2SR) Stereoisomers in СН2Сl2

Authors: Il’in E.G.¹, Parshakov A.S.¹, Privalov V.I.¹, Churakov A.V.¹, Bodrin G.V.², Goryunov E.I.²
Affiliations:
1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Issue: Vol 50, No 2 (2024)
Pages: 92-99
Section: Articles
URL: https://journals.rcsi.science/0132-344X/article/view/261607
DOI: https://doi.org/10.31857/S0132344X24020032
EDN: https://elibrary.ru/OSCMYY
ID: 261607

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Abstract
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Abstract

The monodentate phosphoryl-containing ligand 1-Ac-2-[Ph₂P(O)]-cyclohexane (L) bearing two asymmetric carbon atoms is synthesized. The study of its crystal structure shows that L is a racemic mixture of (1R,2S) and (1S,2R) stereoisomers. The complex formation of L with TiF₄ in СН₂Сl₂ is studied by ¹⁹F{1Н} and ³¹Р{1Н} NMR spectroscopy. The compositions of the complexes formed in the solution are determined. Racemic and meso-diastereomers of the octahedral complex cis-TiF₄L₂ are formed in the solution as found by an analysis of the ¹⁹F and ³¹Р NMR spectra taking into account the concept of heterotropy of organic compounds. The influence of the optical configuration of stereoisomers of the monodentate ligand coexisting in the coordination sphere of the [MF₄L₂] octahedral tetrafluoro complexes of transition d⁰ metals on the chemical shifts of the fluorine atoms arranged in the trans positions relative to each other is shown. In the meso-diastereomer of cis-TiF⁴L₂, this results in a nonequivalence of the fluorine atoms on the F–Ti–F' ordinate of the octahedron, and the spin-spin coupling constant JFF' = 286.1 Hz is observed in the 19F{1H} NMR spectrum.

Keywords

titanium tetrafluoride, complex formation, NMR, stereochemistry

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About the authors

E. G. Il’in

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: eg_ilin@mail.ru
Russian Federation, Moscow

A. S. Parshakov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow

V. I. Privalov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow

A. V. Churakov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow

G. V. Bodrin

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow

E. I. Goryunov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow

References

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2. Fig. 1. The molecular structure of the ligand L. Thermal ellipsoids are shown with a 50% probability.

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3. Fig. 2. NMR spectrum of 31P{1H} 0.1 M ligand solution in L-PhCHMeNH2.

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4. Fig. 3. Temperature dependence of NMR spectra of 19F{1H} TiF4 +2L solution in CH2Cl2. A, A' – lines of racemic, B, B', B" – meso-diastereomers of cis-TiF4L2. The B–line is trans- TiF4L2.

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5. Fig. 4. Temperature dependence of NMR spectra of 31P{1H} TiF4+2L solution in CH2Cl2. A is the signal of trans-TiF4L2, B, C are the lines of racemic and meso-diastereoisomers of cis-TiF4L2, D is the signal of a free ligand.