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

作者: 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
隶属关系:
1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
期: 卷 50, 编号 2 (2024)
页面: 92-99
栏目: Articles
URL: https://rjonco.com/0132-344X/article/view/667617
DOI: https://doi.org/10.31857/S0132344X24020032
EDN: https://elibrary.ru/OSCMYY
ID: 667617

如何引用文章

全文:

开放存取

##reader.subscriptionAccessGranted##
受限制的访问

订阅存取

详细
全文:
作者简介
参考
补充文件
统计

详细

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.

关键词

titanium tetrafluoride, complex formation, NMR, stereochemistry

全文:

作者简介

E. Il’in

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

编辑信件的主要联系方式.
Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

A. Parshakov

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

Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

V. Privalov

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

Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

A. Churakov

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

Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

G. Bodrin

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

E. Goryunov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
俄罗斯联邦, Moscow

参考

Safiulina A. M., Matveeva A. G., Evtushenko A. V. et al. // Russ. J. Gen. Chem. 2015. V. 85. № 9. P. 2128.
Goryunov E. I., Bodrin G. V., Goryunova I. B. et al. // Russ. Chem. Bull. 2013. № 3. P. 779.
Il’in E. G., Parshakov A. S., Yarzhemskii V. G. et al. // Dokl. Ross. Akad. Nauk. 2015. V. 465. № 3. P. 314.
Il’in E. G., Parshakov A. S., Danilov V. V. et al. // Dokl. Ross. Akad. Nauk. 2016. V. 471. № 2. P. 163.
Il’in E. G., Parshakov A. S., Danilov V. V. et al. // Russ. J. Coord. Chem. 2018. V. 44. P. 619. https://doi.org/10.1134/S1070328418100068
Il’in E. G., Parshakov A. S., Privalov V. I. et al. // Dokl. Ross. Akad. Nauk. 2016. V. 467. № 5. P. 547.
Il’in E. G., Parshakov A. S., Aleksandrov G. G. et al. // Dokl. Ross. Akad. Nauk. 2016. V. 470. № 2. P. 176.
Il’in E. G., Kovalev V. V., and Nifant’ev E. E. // Dokl. Ross. Akad. Nauk. 2018. V. 479. № 3. P. 283.
Il’in E. G., Parshakov A. S., Danilov V. V. et al. // Russ. J. Coord. Chem. 2019. V. 45. P. 340. https://doi.org/10.1134/S1070328419030035
Parshakov A. S., Privalov V. I. et al. // Russ. J. Coord. Chem. 2019. V. 45. P. 667. https://doi.org/10.1134/S1070328419090057
Krause L., Herbst-Irmer R., Sheldrick G. M., and Stalke D. J. // Appl. Crystallogr. 2015. V. 48. № 1. P. 3. https://doi.org/10.1107/S1600576714022985
Sheldrick G. M. // Acta Crystallogr., Sect. C: Struct. Chem. 2015. V. 71. № 1. P. 3. https://doi.org/10.1107/S2053229614024218
Groom C. R., Bruno I. J., Lightfoot M. P., and Ward S. C. // Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater. 2016. V. 72. P. 171. https://doi.org/10.1107/S2052520616003954.14
Buslaev Yu.A, and Ilyin E. G. // J. Fluorine Chem. 1984. V. 25. № 1. P. 57.
Potapov V. M. Stereokhimiya (Stereochemistry). Moscow: Khimiya, 1988.
Gaudemer A., Minkin V. I., and Jacques J. // Stereochemistry Fundamental and Methods. V. 1. Kagan H. B., Ed. Stuttgart, 1977. P. 73.
Eliel E. L., Wilen S. H., and Doile M. P. Basic Organic Stereochemistry. New York: Wiley, 2001.
Mislow K, and Raban M. Topics in Stereochemistry // Allinger N. L., and Eliel E. L., Eds. New York: Wiley-Interscience, 1967. V. 1.

补充文件

附件文件

动作

1. JATS XML

下载

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

下载 (170KB)

索引源数据

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

下载 (60KB)

索引源数据

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.

下载 (130KB)

索引源数据

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.