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C–F Bond Cleavage Reactions with Beryllium, Magnesium, Gallium, Hafnium, and Thorium Halides
Author(s) -
Dankert Fabian,
Deubner H. Lars,
Müller Matthias,
Buchner Magnus R.,
Kraus Florian,
von Hänisch Carsten
Publication year - 2020
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201900297
Subject(s) - gallium , chemistry , thorium , halide , hafnium , beryllium , stoichiometry , magnesium , crystal structure , inorganic chemistry , bond cleavage , cleavage (geology) , x ray crystallography , crystallography , zirconium , diffraction , catalysis , uranium , organic chemistry , materials science , physics , optics , metallurgy , fracture (geology) , composite material
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 2 Me 4 ) 2 ( I ) yields the carbenium ion containing compounds [Ph‐C(O 2 Si 2 Me 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.