- C–F Bond Cleavage Reactions with Beryllium, Magnesium, Gallium, Hafnium, and Thorium Halides
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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 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.
- Dankert, Fabian,Deubner, H. Lars,Müller, Matthias,Buchner, Magnus R.,Kraus, Florian,von H?nisch, Carsten
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p. 1501 - 1507
(2020/02/20)
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- New solid solutions based on Bi10M3X18 and Bi6X7 (M = Zr, Hf; X = Cl, Br)
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The Bi10Hf3Cl18-xBr, and Bi 10Zr3Cl18-xBrx(x = 4.5, 9, 13.5) and Bi6Cl7-xBrx (x = 1.75, 3.5, 5.25) solid solutions containing Bi95+ homopolycations and mixed chloride-bromide anions have been obtained by the ampoule method. The unit cell parameters of these samples have been determined. The unit cell parameters are a linear function of the percentage (at. %) of the substituted chlorine, which indicates that these systems form a continuous series of solid solutions. Analogous solid solutions Bi10Hf3Br18-xI x and Bi10Zr3Br18-xIx (x = 4.5, 9, 13.5) are not formed.
- Savilov,Kuznetsov,Donets,Popovkin
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p. 335 - 338
(2008/10/08)
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- Arene Derivatives of Zirconium(II) and Hafnium(II)
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The anhydrous tetrahalides MX4 (M = Zr or Hf, X = Br or I) were prepared by treating M(BH4)4 with dry HX in n-heptane as solvent, followed by sublimation under reduced pressure.The reaction of ZrCl4 with Al-AlCl3-aromatic hydrocarbon systems led to soluti
- Calderazzo, Fausto,Pallavicini, Piersandro,Pampaloni, Guido
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p. 1813 - 1818
(2007/10/02)
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- Process for the preparation of acetic anhydride
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Acetic anhydride is prepared from methyl acetate and/or dimethyl ether in carbonylation processes comprising the use of a halide, carbon monoxide and a Group VIII noble metal in the presence of promoters comprising metallic hafnium and an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent, or an arsine of the formula: STR1 wherein R and R1 are monocyclic aryl groups or alkyl groups and R2 is the radical STR2 a monocyclic aryl group or an alkyl group, and wherein R3 and R4 are each a monocyclic aryl group or an alkyl group, n being zero or a digit from 1-20.
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