M. A. Shmelev, G. A. Razgonyaeva, D. S. Yambulatov, A. G. Starikov, A. A. Sidorov, I. L. Eremenko
{"title":"五氟苯甲酸、2,3,4,5- 和 2,3,5,6-Tetrafluorobenzoate 阴离子中的取代基对镉络合物结构的影响","authors":"M. A. Shmelev, G. A. Razgonyaeva, D. S. Yambulatov, A. G. Starikov, A. A. Sidorov, I. L. Eremenko","doi":"10.1134/S1070328423601486","DOIUrl":null,"url":null,"abstract":"<p>New cadmium 2,3,4,5-tetrafluorobenzoate (6HTfb) and 2,3,5,6-tetrafluorobenzoate (4Htfb) complexes, [Cd(6HTfb)(H<sub>2</sub>O)<sub>3</sub>]<sub><i>n</i></sub><i>·</i>(6HTfb)<i>·</i>2<i>n</i>H<sub>2</sub>O (<b>I</b>), [Cd<sub>3</sub>(Phen)<sub>2</sub>(6HTfb)<sub>6</sub>] (<b>II</b>, Phen = 1,10-phenanthroline), [Cd<sub>2</sub>(Phen)<sub>2</sub>(4Htfb)<sub>4</sub>]<sub><i>n</i></sub>·2<i>n</i>H<sub>2</sub>O (<b>III</b>), and [Cd(Phen)<sub>2</sub>(4Htfb)<sub>2</sub>] (<b>IV</b>), were synthesized. Analysis of the obtained results and published data demonstrated that a decrease in the number of fluorine substituents is unfavorable for the formation of coordination polymers comprising stacked alternating fluorinated and non-fluorinated aromatic moieties. In the case of 2,4,5-trifluorobenzoate complex, a typical trivial structure of the binuclear cadmium complex with ligand-shielded metal core is formed. The synthesis of 2,3,4,5- and 2,3,5,6-tetrafluorobenzoate complexes produced an intermediate situation and demonstrated that the structure of complex formation products is affected by not only the number, but also the positions of fluorine substituents. Using quantum chemical calculations, it was shown that the formation of coordination polymers requires a molecular precursor with a Chinese lantern structure stable in solutions, while the formation of unusual flattened binuclear complexes with additionally coordinated water molecules requires doubly bridged binuclear complexes able to switch to a conformation with exposed coordinatively unsaturated metal centers.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effect of Substituents in the Pentafluorobenzoate and 2,3,4,5- and 2,3,5,6-Tetrafluorobenzoate Anions on the Structure of Cadmium Complexes\",\"authors\":\"M. A. Shmelev, G. A. Razgonyaeva, D. S. Yambulatov, A. G. Starikov, A. A. Sidorov, I. L. Eremenko\",\"doi\":\"10.1134/S1070328423601486\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>New cadmium 2,3,4,5-tetrafluorobenzoate (6HTfb) and 2,3,5,6-tetrafluorobenzoate (4Htfb) complexes, [Cd(6HTfb)(H<sub>2</sub>O)<sub>3</sub>]<sub><i>n</i></sub><i>·</i>(6HTfb)<i>·</i>2<i>n</i>H<sub>2</sub>O (<b>I</b>), [Cd<sub>3</sub>(Phen)<sub>2</sub>(6HTfb)<sub>6</sub>] (<b>II</b>, Phen = 1,10-phenanthroline), [Cd<sub>2</sub>(Phen)<sub>2</sub>(4Htfb)<sub>4</sub>]<sub><i>n</i></sub>·2<i>n</i>H<sub>2</sub>O (<b>III</b>), and [Cd(Phen)<sub>2</sub>(4Htfb)<sub>2</sub>] (<b>IV</b>), were synthesized. Analysis of the obtained results and published data demonstrated that a decrease in the number of fluorine substituents is unfavorable for the formation of coordination polymers comprising stacked alternating fluorinated and non-fluorinated aromatic moieties. In the case of 2,4,5-trifluorobenzoate complex, a typical trivial structure of the binuclear cadmium complex with ligand-shielded metal core is formed. The synthesis of 2,3,4,5- and 2,3,5,6-tetrafluorobenzoate complexes produced an intermediate situation and demonstrated that the structure of complex formation products is affected by not only the number, but also the positions of fluorine substituents. Using quantum chemical calculations, it was shown that the formation of coordination polymers requires a molecular precursor with a Chinese lantern structure stable in solutions, while the formation of unusual flattened binuclear complexes with additionally coordinated water molecules requires doubly bridged binuclear complexes able to switch to a conformation with exposed coordinatively unsaturated metal centers.</p>\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2024-05-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1070328423601486\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S1070328423601486","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Effect of Substituents in the Pentafluorobenzoate and 2,3,4,5- and 2,3,5,6-Tetrafluorobenzoate Anions on the Structure of Cadmium Complexes
New cadmium 2,3,4,5-tetrafluorobenzoate (6HTfb) and 2,3,5,6-tetrafluorobenzoate (4Htfb) complexes, [Cd(6HTfb)(H2O)3]n·(6HTfb)·2nH2O (I), [Cd3(Phen)2(6HTfb)6] (II, Phen = 1,10-phenanthroline), [Cd2(Phen)2(4Htfb)4]n·2nH2O (III), and [Cd(Phen)2(4Htfb)2] (IV), were synthesized. Analysis of the obtained results and published data demonstrated that a decrease in the number of fluorine substituents is unfavorable for the formation of coordination polymers comprising stacked alternating fluorinated and non-fluorinated aromatic moieties. In the case of 2,4,5-trifluorobenzoate complex, a typical trivial structure of the binuclear cadmium complex with ligand-shielded metal core is formed. The synthesis of 2,3,4,5- and 2,3,5,6-tetrafluorobenzoate complexes produced an intermediate situation and demonstrated that the structure of complex formation products is affected by not only the number, but also the positions of fluorine substituents. Using quantum chemical calculations, it was shown that the formation of coordination polymers requires a molecular precursor with a Chinese lantern structure stable in solutions, while the formation of unusual flattened binuclear complexes with additionally coordinated water molecules requires doubly bridged binuclear complexes able to switch to a conformation with exposed coordinatively unsaturated metal centers.
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.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
