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

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 BeBr2 / GaBr3 or MgBr2 / GaBr3 mixtures as well as neat GaI3 with α,α,α‐trifluorotoluene in the presence of (OSi2Me4)2 (...

Full description

Saved in:
Bibliographic Details
Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2020-09, Vol.646 (18), p.1501-1507
Main Authors: Dankert, Fabian, Deubner, H. Lars, Müller, Matthias, Buchner, Magnus R., Kraus, Florian, von Hänisch, Carsten
Format: Article
Language:English
Subjects:
Actinides
Beryllium
Carbenium ions
Cleavage
Crystallography
C–F bond cleavage
Defluorination
Fluorine
Gallium
Hafnium iodides
Halides
Lewis acids
Magnesium compounds
NMR
Nuclear magnetic resonance
Silicon
Thorium
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 BeBr2 / GaBr3 or MgBr2 / GaBr3 mixtures as well as neat GaI3 with α,α,α‐trifluorotoluene in the presence of (OSi2Me4)2 (I) yields the carbenium ion containing compounds [Ph‐C(O2Si2Me4)][GaX4] (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 BeI2, HfI4 or ThI4 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.
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.201900297