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

IF 1.1 3区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR
E. G. Il’in, A. S. Parshakov, V. I. Privalov, A. V. Churakov, G. V. Bodrin, E. I. Goryunov
{"title":"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","authors":"E. G. Il’in,&nbsp;A. S. Parshakov,&nbsp;V. I. Privalov,&nbsp;A. V. Churakov,&nbsp;G. V. Bodrin,&nbsp;E. I. Goryunov","doi":"10.1134/S1070328423700719","DOIUrl":null,"url":null,"abstract":"<p>The monodentate phosphoryl-containing ligand 1-Ac-2-[Ph<sub>2</sub>P(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 TiF<sub>4</sub> in СН<sub>2</sub>Сl<sub>2</sub> is studied by <sup>19</sup>F{<sup>1</sup>Н} and <sup>31</sup>Р{<sup>1</sup>Н} NMR spectroscopy. The compositions of the complexes formed in the solution are determined. Racemic and <i>meso-</i>diastereomers of the octahedral complex <i>cis</i>-TiF<sub>4</sub>L<sub>2</sub> are formed in the solution as found by an analysis of the <sup>19</sup>F and <sup>31</sup>Р 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 [MF<sub>4</sub>L<sub>2</sub>] octahedral tetrafluoro complexes of transition <i>d</i><sup>0</sup> metals on the chemical shifts of the fluorine atoms arranged in the <i>trans</i> positions relative to each other is shown. In the <i>meso</i>-diastereomer of <i>cis</i>-TiF<sub>4</sub>L<sub>2</sub>, this results in a nonequivalence of the fluorine atoms on the F–Ti–F' ordinate of the octahedron, and the spin-spin coupling constant <i>J</i><sub>FF'</sub> = 286.1 Hz is observed in the <sup>19</sup>F{<sup>1</sup>H} NMR spectrum.</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 2","pages":"137 - 144"},"PeriodicalIF":1.1000,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stereochemistry of the cis-Tetrafluoro Complexes of Titanium with 1-Ac-2-[Ph2P(O)]-Cyclohexane (1RS,2SR) Stereoisomers in СН2Сl2\",\"authors\":\"E. G. Il’in,&nbsp;A. S. Parshakov,&nbsp;V. I. Privalov,&nbsp;A. V. Churakov,&nbsp;G. V. Bodrin,&nbsp;E. I. Goryunov\",\"doi\":\"10.1134/S1070328423700719\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The monodentate phosphoryl-containing ligand 1-Ac-2-[Ph<sub>2</sub>P(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 TiF<sub>4</sub> in СН<sub>2</sub>Сl<sub>2</sub> is studied by <sup>19</sup>F{<sup>1</sup>Н} and <sup>31</sup>Р{<sup>1</sup>Н} NMR spectroscopy. The compositions of the complexes formed in the solution are determined. Racemic and <i>meso-</i>diastereomers of the octahedral complex <i>cis</i>-TiF<sub>4</sub>L<sub>2</sub> are formed in the solution as found by an analysis of the <sup>19</sup>F and <sup>31</sup>Р 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 [MF<sub>4</sub>L<sub>2</sub>] octahedral tetrafluoro complexes of transition <i>d</i><sup>0</sup> metals on the chemical shifts of the fluorine atoms arranged in the <i>trans</i> positions relative to each other is shown. In the <i>meso</i>-diastereomer of <i>cis</i>-TiF<sub>4</sub>L<sub>2</sub>, this results in a nonequivalence of the fluorine atoms on the F–Ti–F' ordinate of the octahedron, and the spin-spin coupling constant <i>J</i><sub>FF'</sub> = 286.1 Hz is observed in the <sup>19</sup>F{<sup>1</sup>H} NMR spectrum.</p>\",\"PeriodicalId\":759,\"journal\":{\"name\":\"Russian Journal of Coordination Chemistry\",\"volume\":\"50 2\",\"pages\":\"137 - 144\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2024-05-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Journal of Coordination Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1070328423700719\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S1070328423700719","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0

摘要

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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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

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

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

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.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Russian Journal of Coordination Chemistry
Russian Journal of Coordination Chemistry 化学-无机化学与核化学
CiteScore
2.40
自引率
15.80%
发文量
85
审稿时长
7.2 months
期刊介绍: Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信