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

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-05-08 DOI:10.1134/S1070328423700719

E. G. Il’in, A. S. Parshakov, V. I. Privalov, A. V. Churakov, G. V. Bodrin, E. I. Goryunov

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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 J_FF' = 286.1 Hz is observed in the ¹⁹F{¹H} NMR spectrum.

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钛与 1-Ac-2-[Ph2P(O)]-环己烷（1RS,2SR）立体异构体在 СН2Сl2 中的顺式四氟络合物的立体化学性质

摘要合成了含有两个不对称碳原子的单齿含磷配体 1-Ac-2-[Ph2P(O)]-环己烷（L）。对其晶体结构的研究表明，L 是 (1R,2S) 和 (1S,2R) 立体异构体的外消旋混合物。19F{1Н} 和 31Р{1Н} 核磁共振光谱研究了 L 与 TiF4 在 СН2Сl2 中形成的复合物。核磁共振光谱进行了研究。确定了在溶液中形成的复合物的成分。通过分析 19F 和 31Р NMR 光谱，并考虑到有机化合物的各向异性概念，发现在溶液中形成了八面体复合物 cis-TiF4L2 的外消旋体和中消旋体。在过渡 d0 金属的 [MF4L2] 八面体四氟配合物的配位层中共存的单齿配体的立体异构体的光学构型对反式位置上的氟原子的化学位移的影响。在顺式-TiF4L2 的中间非对映异构体中，这导致八面体 F-Ti-F' 轴上的氟原子不等价，并在 19F{1H} NMR 光谱中观察到自旋-自旋耦合常数 JFF' = 286.1 Hz。NMR 光谱中观察到。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.