Katharina Tölke, Sven Porath, Beate Neumann, Hans-Georg Stammler, Berthold Hoge
{"title":"第一个主族元素路易斯酸亚硫酰氯加合物及其化学性质。","authors":"Katharina Tölke, Sven Porath, Beate Neumann, Hans-Georg Stammler, Berthold Hoge","doi":"10.1002/anie.202408741","DOIUrl":null,"url":null,"abstract":"<p><p>Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR<sub>4</sub>]<sup>-</sup>, behave as weakly coordinating anions, neutral gallanes and indanes, MR<sub>3</sub>, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and -indate, [M(C<sub>2</sub>F<sub>5</sub>)<sub>4</sub>]<sup>-</sup> (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub>(OH<sub>2</sub>)<sub>2</sub>] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub>D], with the weak donor molecules (D) SOCl<sub>2</sub> and Me<sub>3</sub>SiF. The effective Lewis acidities of Ga(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> and In(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> were experimentally determined by the (modified) Gutmann-Beckett method and their catalytic potential is showcased.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"First Main-Group Element Lewis Acid Thionyl Chloride Adduct and its Chemistry.\",\"authors\":\"Katharina Tölke, Sven Porath, Beate Neumann, Hans-Georg Stammler, Berthold Hoge\",\"doi\":\"10.1002/anie.202408741\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR<sub>4</sub>]<sup>-</sup>, behave as weakly coordinating anions, neutral gallanes and indanes, MR<sub>3</sub>, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and -indate, [M(C<sub>2</sub>F<sub>5</sub>)<sub>4</sub>]<sup>-</sup> (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub>(OH<sub>2</sub>)<sub>2</sub>] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub>D], with the weak donor molecules (D) SOCl<sub>2</sub> and Me<sub>3</sub>SiF. The effective Lewis acidities of Ga(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> and In(C<sub>2</sub>F<sub>5</sub>)<sub>3</sub> were experimentally determined by the (modified) Gutmann-Beckett method and their catalytic potential is showcased.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2024-10-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/anie.202408741\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/9/5 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202408741","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/9/5 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
First Main-Group Element Lewis Acid Thionyl Chloride Adduct and its Chemistry.
Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]-, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and -indate, [M(C2F5)4]- (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally determined by the (modified) Gutmann-Beckett method and their catalytic potential is showcased.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.