C-F Bond Cleavage Reactions with Beryllium, Magnesium, Gallium, Hafnium, and Thorium Halides

Fabian Dankert; H. Lars Deubner; Matthias Müller; Magnus R. Buchner; Florian Kraus; Carsten von H?nisch

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C-F Bond Cleavage Reactions with Beryllium, Magnesium, Gallium, Hafnium, and Thorium Halides

机译：用铍，镁，镓，铪和卤化物的C-F粘合切割反应

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The work describes unexpected stoichiometric C-F bond cleavage reactions of beryllium, magnesium, gallium, hafnium and thorium halides with α,α,α-trifluorotoluene. The reaction of BeBr_2 / GaBr_3 or MgBr_2 / GaBr_3 mixtures as well as neat GaI_3 with α,α,α- trifluorotoluene in the presence of (OSi_2Me_4)_2 (I) yields the carbenium ion containing compounds [Ph-C(O_2Si_2Me_4)][GaX_4] (X = Br: 1, X = I/F: 2). Both compounds were successfully characterized and a defluorination type reaction under incorporation of a siloxy unit was observed. Compound 1 was also characterized by single-crystal X-ray diffraction analysis. The conversion of α,α,α-trifluorotoluene with BeI_2, HfI_4 or ThI_4 turned out to be a halodefluorination-type reaction with formation of α,α,α-triiodotoluene (3). An adequate NMR spectroscopic and the X-ray crystallographic characterization of 3 were performed for the first time.

机译：这项工作描述了铍、镁、镓、铪和钍卤化物与α、α、α-三氟甲苯的意外化学计量C-F键断裂反应。BeBr_2/GaBr_3或MgBr_2/GaBr_3混合物以及纯GaI_3与α，α，α-三氟甲苯在（OSi_2Me_4）_2（I）存在下反应生成含碳离子的化合物[Ph-C（O_2Si_2Me_4）][GaX_4]（X=Br:1，X=I/F:2）。这两种化合物均已成功表征，并观察到在掺入硅氧基单元的情况下发生脱氟反应。化合物1还通过单晶X射线衍射分析进行了表征。α，α，α-三氟甲苯与BeI_2，HfI_4或ThI_4的转化结果证明是一个卤代脱氟型反应，生成α，α，α-三碘甲苯（3）。首次对3进行了充分的核磁共振波谱和X射线晶体学表征。

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来源
《Zeitschrift fur Anorganische und Allgemeine Chemie》 |2020年第18期|共7页
作者
Fabian Dankert; H. Lars Deubner; Matthias Müller; Magnus R. Buchner; Florian Kraus; Carsten von H?nisch;
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作者单位

Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW) Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

Fachbereich Chemie: Anorganische Chemie - Fluorchemie Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

Fachbereich Chemie: Anorganische Chemie - Nachwuchsgruppe Berylliumchemie Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

Fachbereich Chemie: Anorganische Chemie - Nachwuchsgruppe Berylliumchemie Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

Fachbereich Chemie: Anorganische Chemie - Fluorchemie Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW) Philipps-Universit?t Marburg Hans-Meerwein Str. 4 35032 Marburg Germany;

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正文语种 eng
中图分类化学;
关键词
Lewis acids; C-F bond cleavage; Carbenium ions; Actinides; Silicon; Fluorine; Defluorination;

机译：路易斯酸;C-F键切割;碳离子;散光;硅;氟;偏氟化;

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C-F Bond Cleavage Reactions with Beryllium, Magnesium, Gallium, Hafnium, and Thorium Halides

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